Method for the preparation of substituted thiolactones, new substituted thiolactones and uses thereof

ABSTRACT

The invention relates to a method for preparing substituted thiolactones of formula (I), new substituted thiolactones of formula (I′) that can be obtained by carrying out said method, and the use of substituted thiolactones of formula (I) or (I′) for synthesizing polymers or functionalizing surfaces or polymers.

The present invention relates to the field of thiolactones.

More particularly, the present invention relates to a process forpreparing substituted thiolactones of formula (I), novel substitutedthiolactones of formula (I′) able to be obtained by carrying out thisprocess, the use of substituted thiolactones of formula (I) or offormula (I′) for the preparation of polymers or for surfacefunctionalization or polymer functionalization.

Thiolactones are heterocyclic compounds analogous to lactones, in whichan oxygen atom is replaced by a sulfur atom. The sulfur atom is locatedin the ring and is adjacent to a carbonyl group. The heterocycle ofthiolactones may be substituted by at least one chemical group, inparticular by an alkyl or aryl group.

Several processes for synthesizing thiolactones have already beenproposed.

F. Korte et al. (Chem. Ber., 1961, 94, 1966), for example, proposedeither carrying out thermal cyclization of a mercaptocarboxylic acidbearing an alkyl substituent, or directly substituting a thiolactonewith an alkyl radical in the presence of an alkyl halide group (R—X) andlithium dialkylamide (LiNR′₂). These two synthesis routes may berepresented by the following reaction scheme (1):

According to this synthesis route, only the final step of thermalcyclization is general, with the preceding steps leading to themercaptocarboxylic acid and the reagents used being specific to the typeof R group that it is desired to introduce to the heterocycle. Moreover,these two synthesis routes do not make it possible to introducesubstituents other than alkyl groups.

A more recent synthesis process makes it possible to obtain thiolactoneshaving alkyl or aryl groups (J.-J. Filippi et al., Tet. Lett., 2006, 47,6067). This process is based on a process of catalytic isomerization ofa thionolactone to a thiolactone in the presence of boron trifluoride(BF₃) and diethyl ether (Et₂O) in an organic solvent such as toluene atreflux, according to the following reaction scheme (2):

However, this process uses a catalyst of Lewis acid type (borontrifluoride) and cannot be readily used for the synthesis ofthiolactones bearing substituents other than alkyl or phenyl groups,such as complex organic functions and/or those that are incompatiblewith this type of catalyst. Moreover, the isolated thiolactone yieldsare often low. Finally, this process requires the synthesis of startingthionolactones from the corresponding lactones.

There is therefore a need for a process which makes it possible tosynthesize thiolactones substituted by various functional groups in aflexible and simple manner, and according to a process which is bothefficient and economical.

Therefore, the first subject of the present invention is a process forpreparing substituted thiolactones of the following formula (I):

wherein:

-   -   A¹ and A², which are identical or different, represent a        hydrogen atom or a fluorine atom,    -   Y represents a hydrogen atom or a group selected from alkyl,        hydroxyalkyl, aryl and cyano groups, or a polymer chain;    -   L is a linker arm,    -   m is an integer equal to 0 or 1,    -   T represents CH₂, —O— or —NR⁶—, in which R⁶ represents a        hydrogen atom or an alkyl, aryl or aralkyl radical, optionally        substituted by a group selected from the groups: maleimide, a        group of formula:

in which the symbol # is the point of attachment of said group to R⁶ andin which Y has the same meaning as that chosen for the radical Y of theformula (I), OH; P(O)(OR⁷)(OR^(7′)) in which the radicals R⁷ and R^(7′),which are identical or different, represent a hydrogen atom or an alkylradical; C_(n)F_(2n+1) in which n is an integer ranging from 1 to 20;SiR⁸ _(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which areidentical or different, represent a hydrogen atom or an alkyl radicaland p is an integer equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na;B(OR¹⁰)₂, in which the two radicals R¹⁰, which are identical ordifferent, represent a hydrogen atom, an alkyl radical or form acarbon-based ring with the two oxygen atoms to which they are bonded;OR¹¹, in which R¹¹ represents a hydrogen atom or an alkyl, aryl oraralkyl radical; O(C═O)R¹², in which R¹² represents a hydrogen atom oran alkyl, aryl or aralkyl radical; O(C═O)OR¹³, in which R¹³ represents ahydrogen atom or an alkyl, aryl or aralkyl radical;N⁺R¹⁴R^(14′)R^(14″)A⁻, in which the radicals R¹⁴, R^(14′) and R^(14″),which are identical or different, represent a hydrogen atom or an alkyl,aryl or aralkyl radical and A represents a chlorine or bromine atom;NR^(15′)(C═O)R¹⁵, in which the radicals R¹⁵ and R^(15′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical or are connected together and form a ring such as a pyrrolidoneor caprolactam ring; NR^(16′)(C═O)OR¹⁶, in which R¹⁶ et R^(16′), whichare identical or different, represent a hydrogen atom or an alkyl, arylor aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS;OCH₂-epoxy; COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl,aryl or aralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), whichare identical or different, represent a hydrogen atom or an alkyl oraryl radical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical;azide N₃ and alkyne,

-   -   e is an integer equal to 0 or 1,

it being understood that:

1) when A¹=A²=H and e=0, then W represents a hydrogen atom and Z¹represents a group selected from the groups alkyl; aryl;P(O)(OR⁷)(OR^(7′)), in which the radicals R⁷ and R^(7′), which areidentical or different, represent a hydrogen atom or an alkyl radical;C_(n)F_(2n+1) in which n is an integer ranging from 1 to 20; SiR⁸_(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which are identical ordifferent, represent a hydrogen atom or an alkyl radical and p is aninteger equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na; B(OR¹⁰)₂, inwhich the two radicals R¹⁰, which are identical or different, representa hydrogen atom, an alkyl radical or form a carbon-based ring with thetwo oxygen atoms to which they are bonded; OR¹¹, in which R¹¹ representsa hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R¹², inwhich R¹² represents a hydrogen atom or an alkyl, aryl or aralkylradical; O(C═O)OR¹³, in which R¹³ represents a hydrogen atom or analkyl, aryl or aralkyl radical; N⁺R¹⁴R^(14′)R^(14″)A⁻, in which theradicals R¹⁴, R^(14′) and R^(14″), which are identical or different,represent a hydrogen atom or an alkyl, aryl or aralkyl radical and Arepresents a chlorine or bromine atom; NR^(15′)(C═O)R¹⁵, in which theradicals R¹⁵ and R^(15′), which are identical or different, represent ahydrogen atom or an alkyl or aryl radical or are connected together andform a ring such as a pyrrolidone or caprolactam ring;NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), which are identical ordifferent, represent a hydrogen atom or an alkyl, aryl or aralkylradical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH₂-epoxy;COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl, aryl oraralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical; azideN₃ and alkyne; and a thiolactone ring of formula

in which the symbol # is the point of attachment of the thiolactone ringto L and in which Y has the same meaning as that chosen for the radicalY of the formula (I),

2) when A¹=A²=H, m=1 and e=0, then W represents a hydrogen atom and Z¹may also represent a hydrogen atom;

3) when A¹=A²=H, e=1 and m=0, then Z¹ and W are identical and represent—CH₂— or CO;

4) when A¹=A²=H, e=1, m=1 and T=CH₂ then Z¹=W=—CH₂,

5) when A¹=A²=F, e=0 and m=0, then W represents a fluorine atom and Z¹=For represents a linear or branched chain OC_(q)F_(2q+1) in which q is aninteger ranging from 1 to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integerranging from 0 to 20, OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, orOCF₂CF(CF₃)OC₂F₄CO₂CH₃;

6) when A¹=A²=F, e=1 and m=0, then W=Z¹=CF₂ and T=(CF₂)_(s), with s=aninteger ranging from 1 to 5; and

7) when A¹=H, A²=F, and e=m=0, then W represents a hydrogen atom andZ¹=F or C_(n)F_(2n+1), in which n is an integer ranging from 1 to 20;

said process being characterized in that it comprises at least thefollowing steps:

1) a step during which, in the presence of a radical initiator, axanthate of the following formula (II) is reacted:

wherein:

-   -   R¹, R², R³ and R⁴, which are identical or different, represent a        hydrogen atom or a group chosen from saturated or unsaturated        heterocycloalkyl, alkyl, acyl, aryl, alkene, alkyne, cycloalkyl,        or heterocycloaryl groups and polymer chains, it being        understood that the radicals R¹, R², R³ and R⁴ may also form,        together, a saturated, unsaturated or aromatic cycloalkyl or        heterocycloalkyl group; it being understood that at least one of        the radicals R¹ and R³ is other than a hydrogen atom;    -   Y has the same meaning as in the formula (I) above,    -   X represents NR²⁰, in which R²⁰ represents a hydrogen atom or an        alkyl radical or —O—,    -   R⁵ is chosen from a saturated, unsaturated or aromatic        heterocycloalkyl, alkyl, acyl, aryl, aralkyl or cycloalkyl        group;

with a monomer comprising at least one ethylenic unsaturation of thefollowing formula (III):

wherein:

-   -   A¹ and A², which are identical or different, represent a        hydrogen atom or a fluorine atom,    -   L, m, T and e have the same meaning as in the formula (I) above;

it being understood that:

1) when A¹=A²=H and e=0, then W represents a hydrogen atom and Z²represents a group selected from the groups alkyl; aryl;P(O)(OR⁷)(OR^(7′)), in which the radicals R⁷ and R^(7′), which areidentical or different, represent a hydrogen atom or an alkyl radical;C_(n)F_(2n+1), in which n is an integer ranging from 1 to 20; SiR⁸_(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which are identical ordifferent, represent a hydrogen atom or an alkyl radical and p is aninteger equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na; B(OR¹⁰)₂, inwhich the two radicals R¹⁰, which are identical or different, representa hydrogen atom, an alkyl radical or form a carbon-based ring with thetwo oxygen atoms to which they are bonded; OR¹¹, in which R¹¹ representsa hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R¹², inwhich R¹² represents a hydrogen atom or an alkyl, aryl or aralkylradical; O(C═O)OR¹³, in which R¹³ represents a hydrogen atom or analkyl, aryl or aralkyl radical; N⁺R¹⁴R^(14′)R^(14″)A⁻, in which theradicals R¹⁴, R^(14′) and R^(14″), which are identical or different,represent a hydrogen atom or an alkyl, aryl or aralkyl radical and Arepresents a chlorine or bromine atom; NR^(15′)(C═O)R¹⁵, in which theradicals R¹⁵ and R^(15′), which are identical or different, represent ahydrogen atom or an alkyl or aryl radical or are connected together andform a ring such as a pyrrolidone or caprolactam ring;NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), which are identical ordifferent, represent a hydrogen atom or an alkyl, aryl or aralkylradical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH₂-epoxy;COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl, aryl oraralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical; azideN₃, alkyne and C₂H₃ (i.e. CH═CH₂);

2) when A¹=A²=H, m=1 and e=0, then W represents a hydrogen atom and Z²may also represent a hydrogen atom,

3) when A¹=A²=H, e=1 and m=0, then Z² and W are identical and represent—CH₂— or CO;

4) when A¹=A²=H, e=1, m=1 and T=CH₂, then Z²=W=—CH₂,

5) when A¹=A²=F, e=0 and m=0, then W represents a fluorine atom and Z²=For represents a linear or branched chain OC_(q)F_(2q+1) in which q is aninteger ranging from 1 to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integerranging from 0 to 20, OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, orOCF₂CF(CF₃)OC₂F₄CO₂CH₃; and

6) when A¹=A²=F, e=1 and m=0, then W=Z²=CF₂ and T=(CF₂)_(s), with s=aninteger ranging from 1 to 5;

7) when A¹=H, A²=F, and e=m=0, then W represents a hydrogen atom andZ²=F or C_(n)H_(2n+1), in which n is an integer ranging from 1 to 20;

to form a monoadduct of the following formula (IV):

wherein:

-   -   A¹ and A², which are identical or different, represent a        hydrogen atom or a fluorine atom,    -   R¹, R², R³, R⁴, R⁵, X and Y have the same meaning as in the        formula (II) above,    -   L, m, T and e have the same meaning as in the formula (I) above,

it being understood that:

1) when A¹=A²=H and e=0, then W represents a hydrogen atom and Z³represents a group selected from the groups alkyl; aryl;P(O)(OR⁷)(OR^(7′)), in which the radicals R⁷ and R^(7′), which areidentical or different, represent a hydrogen atom or an alkyl radical;C_(n)F_(2n+1), in which n is an integer ranging from 1 to 20; SiR⁸_(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which are identical ordifferent, represent a hydrogen atom or an alkyl radical and p is aninteger equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na; B(OR¹⁰)₂, inwhich the two radicals R¹⁰, which are identical or different, representa hydrogen atom, an alkyl radical or form a carbon-based ring with thetwo oxygen atoms to which they are bonded; OR¹¹, in which R¹¹ representsa hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R¹², inwhich R¹² represents a hydrogen atom or an alkyl, aryl or aralkylradical; O(C═O)OR¹³, in which R¹³ represents a hydrogen atom or analkyl, aryl or aralkyl radical; N⁺R¹⁴R^(14′)R^(14″)A⁻, in which theradicals R¹⁴, R^(14′) and R^(14″), which are identical or different,represent a hydrogen atom or an alkyl, aryl or aralkyl radical and Arepresents a chlorine or bromine atom; NR^(15′)(C═O)R¹⁵, in which theradicals R¹⁵ and R^(15′), which are identical or different, represent ahydrogen atom or an alkyl or aryl radical or are connected together andform a ring such as a pyrrolidone or caprolactam ring;NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), which are identical ordifferent, represent a hydrogen atom or an alkyl, aryl or aralkylradical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH₂-epoxy;COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl, aryl oraralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical; azideN₃, alkyne, and a group of the following formula (V):

in which the symbol # is the point of attachment of the group of formula(V) to L and R¹, R², R³, R⁴, R⁵ and Y respectively have the same meaningas that chosen for R¹, R², R³, R⁴, R⁵ and Y in the formula (IV),

2) when A¹=A²=H, m=1 and e=0, then W represents a hydrogen atom and Z³may also represent a hydrogen atom,

3) when A¹=A²=H, e=1 and m=0, then Z³ and W are identical and represent—CH₂— or CO;

4) when A¹=A²=H, e=1, m=1 and T=CH₂, then Z³=W=—CH₂,

5) when A¹=A²=F, e=0 and m=0, then W represents a fluorine atom and Z³=For represents a linear or branched chain OC_(q)F_(2q+1) in which q is aninteger ranging from 1 to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integerranging from 0 to 20, OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, orOCF₂CF(CF₃)OC₂F₄CO₂CH₃; and

6) when A¹=A²=F, e=1 and m=0, then W=Z³=CF₂ and T=(CF₂)_(s), with s=aninteger ranging from 1 to 5;

7) when A¹=H, A²=F, and e=m=0, then W represents a hydrogen atom andZ³=F or C_(n)F_(2n+1), in which n is an integer ranging from 1 to 20;

then

2) a step of thermolysis of the monoadduct of formula (IV) obtainedabove in the preceding step, to form a corresponding substitutedthiolactone of formula (I).

The process for preparing the substituted thiolactones of formula (I) inaccordance with the invention may be represented by the followingreaction scheme (3):

By virtue of the process in accordance with the present invention, andas described above, it is now possible to simply and quickly, and with agood yield, obtain thiolactones substituted by various organic groups.

According to a first particularly advantageous embodiment form, theprocess of the invention leads to the formation of a dithiolactone offormula (Ia), in which A¹, A², L, m and Y have the same meaning as informula (I) and W=H, said dithiolactone being obtained according to thereaction scheme (4a)

in which

-   -   the monomer comprising an ethylenic unsaturation of general        formula (IIIa) corresponds to a monomer of formula (III) in        which e=0, Z²=C₂H₃ (i.e. CH═CH₂) and W=H and A¹, A², L and m        having the same meaning as in formula (III),    -   the monoadduct of general formula (IVa) corresponds to a        monoadduct of formula (IV) in which e=0, Z³ is a group of        formula (V) as defined above, in which W=H and A¹, A², L, m, X,        R¹, R², R³, R⁴ and R⁵ have the same meaning as in formula (IV).

According to another particularly advantageous embodiment form, theprocess of the invention leads to the formation of a dithiolactone offormula (Ib), in which A¹, A² and Y have the same definition as informula (I), m=0, W and Z¹=CO, e=1, T=NR⁶, in which R⁶ has the samemeaning as that chosen for the radical R⁶ of formula (I), saiddithiolactone being obtained according to the following reaction scheme(4b):

in which the monomer comprising an ethylenic unsaturation of generalformula (IIIb) corresponds to a monomer of formula (III) in which A¹ andA² have the same meaning as in formula (I), m=0, Z²=W=CO, e=1 and T=NR⁶with R⁶=the same meaning as that chosen for the radical R⁶ of formula(I), and

-   -   the monoadduct of general formula (IVb) corresponds to a        monoadduct of formula (IV) in which m=0, Z³=W=CO, e=1 and T=NR⁶,        with R⁶=an alkyl, aryl, or aralkyl radical substituted by a        maleimide group, and A¹, A², Y, X, R¹, R², R³, R⁴ and R⁵ have        the same definition as in formula (I).

According to the invention, the thiolactones of formula (I) in which A¹and A² represent a hydrogen atom are preferred.

The nature of the linker arm L is not critical. The linker arm L mayespecially be an optionally fluorinated or perfluorinatedhydrocarbon-based chain, in particular optionally fluorinated orperfluorinated linear alkylene, which may be interrupted by one or moreheteroatoms, preferably by one or more oxygen atoms and preferentiallyat least one oxygen atom is in the penultimate position, said optionallyfluorinated or perfluorinated hydrocarbon-based chain having from 1 to100 carbon atoms, preferentially from 1 to 12 carbon atoms, and evenmore preferentially from 1 to 3 carbon atoms.

According to a particularly preferred embodiment form of the invention,the linker arm L is a linear alkylene chain having from 1 to 8 carbonatoms.

The alkyl radicals mentioned for R¹, R², R³, R⁴, R⁵, R⁶, Y and theradicals Z (Z¹, Z² and Z³) may be linear, branched, substituted orunsubstituted and comprise from 1 to 12 carbon atoms. They arepreferably chosen from methyl, ethyl, n-propyl, iso-propyl, n-butyl,2-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl,tert-pentyl, hexyl, n-octyl, iso-octyl, 2-ethyl-1-hexyl,2,2,4-trimethylpentyl, nonyl, decyl, dodecyl and benzyl radicals. Amongsuch radicals, methyl, ethyl, n-propyl, iso-propyl and n-butyl radicalsare most particularly preferred.

For the purposes of the present invention, an acyl group denotes a groupof formula —C(═O)-D, in which D denotes a hydrogen atom or a linear orbranched, saturated or unsaturated hydrocarbon-based chain comprisingfrom 1 to 12 carbon atoms. Among such acyl groups mentioned for R¹, R²,R³, R⁴, R⁵, R⁶, Z¹, Z² and Z³, mention may especially be made of formyl,acetyl, propanoyl pivaloyl groups.

For the purposes of the invention, aryl group is intended to mean amonocyclic or polycyclic aromatic hydrocarbon-based group that isoptionally monosubstituted or polysubstituted. By way of aryl radicalmentioned for R¹, R², R³, R⁴, R⁵, R⁶, Z¹, Z² and Z³, mention may inparticular be made of naphthyl, anthranyl, phenanthryl, o-tolyl,p-tolyl, xylyl, ethylphenyl, mesityl and phenyl groups. Among suchgroups, the phenyl group is particularly preferred.

For the purposes of the present invention, the cycloalkyl group is asaturated cyclic group comprising from 3 to 10 carbon atoms. Among suchcycloalkyl groups mentioned for R¹, R², R³, R⁴, R⁵ and R⁶, mention mayin particular be made of cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl groups.

Still for the purposes of the present invention, a heterocycloalkylgroup is a saturated cyclic group comprising from 3 to 9 carbon atomsand at least one heteroatom chosen from N, O, P, Si and S. Among suchheterocycloalkyl groups mentioned for R¹, R², R³, R⁴, R⁵ and R⁶, mentionmay in particular be made of oxacyclopropanyl, azacyclopropanyl,thiacyclopropanyl, tetrahydrofuranyl, pyrrolidinyl,tetrahydrothiophenyl, tetrahydropyranyl, piperidinyl, piperazinyl andthiacyclohexane groups.

For the purposes of the present invention, a heterocycloaryl group is amonocyclic or polycyclic aromatic group comprising from 5 to 6 carbonatoms and at least one heteroatom chosen from N, O, P, Si and S. Amongsuch heterocycloaryl groups mentioned for R¹, R², R³, R⁴, R⁵ and R⁶,mention may in particular be made of furanyl, thiophenyl, pyrrolyl,pyridinyl, pyranyl, oxazinyl, thazinyl, pyrimidinyl, piperazinyl andthiinyl groups.

In a particular embodiment, R¹, R², R³ and R⁴, which are identical ordifferent, represent a hydrogen atom or an alkyl group, of course withthe proviso, as indicated above, that at least one of the groups R¹ andR³ is other than a hydrogen atom.

According to a particularly preferred embodiment form of the invention,R¹ (respectively R³) is an alkyl group, especially a methyl group, andR³ (respectively R¹) is a hydrogen atom.

Preferably, at least one of the groups R² and R⁴ is other than ahydrogen atom.

Further preferably, R² (respectively R⁴) is an alkyl group, especially amethyl group, and R⁴ (respectively R²) is a hydrogen atom or an alkylgroup, especially a methyl group.

Finally, according to the present invention, polymer chain is intendedto mean any linked sequence of monomer units obtained by a radicalpolymerization process controlled by reversible addition-fragmentation(RAFT/MADIX process as described, for example, by Moad, G. et al., Aust.J. Chem., 2012, 65(8), 985-1076) or atom transfer (ATRP process, i.e.Atom Transfer Radical Polymerization as described, for example, byMatyjaszewski, K., Chem. Rev., 2001, 101(9), 2921-2990), carried outsuch that the terminal monomer unit connected respectively to the sulfuratom of the thiocarbonylthio group (RAFT/MADIX), or halogen (Cl, Br)group for ATRP, is of acrylate type, for example methyl acrylate, oracrylamido, such as N-isopropylacrylamide.

For the purposes of the present invention, in the compounds of formula(I), (III) or (IIIa) and (IV) or (IVa), when e=0 then T is absent and Wand, respectively, Z¹, Z² and Z³ are not connected.

The process in accordance with the invention is preferably carried outfor preparing substituted thiolactones of formula (I) as defined above,in which:

-   -   Z¹ is preferably a group chosen from the groups        P(O)(OR⁷)(OR^(7′)), in particular a dimethylphosphonate group        (R⁷=R^(7′)=—CH₃) or diethylphosphonate group        (R⁷=R^(7′)=—CH₂CH₃); C_(n)F_(2n+1) in which n is preferably an        integer ranging from 1 to 10; B(OR¹⁰)₂; OR¹¹; SiR⁸        _(p)(OR⁹)_(3-p); NR^(15′)(C═O)R¹⁵, in which R^(15′) is a        hydrogen atom and NR^(16′)(C═O)OR¹⁶, in which R^(16′) is a        hydrogen atom, and/or    -   Y is preferably a hydrogen atom or a group chosen from an alkyl        radical, in particular methyl and hydroxymethyl.

According to a particularly preferred embodiment form of the invention,R⁵ is an alkyl group, especially a methyl group.

The process in accordance with the invention is preferably carried outto prepare thiolactones of formula (I) in which e=0, m=1 and Z¹ is otherthan a hydrogen atom.

According to a particularly advantageous embodiment form, the process ofthe invention leads to the formation of a thiolactone of formula (I)chosen from:

-   dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1);-   diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate    (TL2);-   diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3);-   3-methyl-5-pentyl-dihydrothiophen-2(3H)-one (TL4);-   5-pentyl-dihydrothiophen-2(3H)-one (TL5);-   3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6);-   3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione    (TL7);-   3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8);-   (4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid (TL9);-   ((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid    (TL10);-   (5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid (TL11);-   3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one (TL12);-   5-(trimethoxysilyl)dihydrothiophen-2(3H)-one (TL13);-   tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate    (TL14);-   tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate (TL15);-   3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one (TL16);-   5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one (TL17);-   3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one    (TL18);-   (5-oxo-tetrahydrothiophen-2-yl)phosphonic acid (TL19);-   5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one    (TL20);-   5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL21);-   5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL22);-   dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one    (TL23);-   5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL24);-   5-(9-bromononyl)3-methyldihydrothiophen-2(3H)-one (TL25);-   5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL26),    and-   5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL27).

When they are not commercially available, the xanthates of formula (II)may be obtained according to a process analogous to that used ininternational application WO 2004/024681 and consisting in:

a) in a first step, reacting, in an organic solvent, an alcohol offollowing formula (VI):

in which the radicals R¹, R², R³ and R⁴ have the same meaning as in thecompounds of formula (II) above

with carbon disulfide in the presence of a base to obtain a salt offollowing formula (VII):

in which the radicals R¹, R², R³ and R⁴ have the same meaning as in thexanthate of formula (II) above, and J⁺ is a cation chosen from alkalimetals, such as a K⁺ or Na⁺ cation, then

b) in a second step, reacting the compound of formula (VII) obtainedabove in the preceding step with a compound of following formula (VIII):

in which R⁵ and X have the same meaning as in the xanthate of formula(II) above, to obtain a corresponding xanthate of formula (II).

The first step a) of preparing a compound of formula (VII) is preferablycarried out at room temperature in an organic solvent such astetrahydrofuran and using a strong base, preferably potassium hydroxide.The duration of step a) is generally from approximately 20 to 24 hours.

The second step b) of preparing a xanthate of formula (II) is preferablycarried out in an organic solvent such as acetone and in an ice bath,since the reaction of addition of the compound of formula (VIII) ishighly exothermic.

Once the addition of the compound of formula (VIII) has finished, thereaction is preferably carried out at room temperature for a duration ofapproximately 2 to 4 hours. When the reaction has finished, the xanthateof formula (II) thus obtained is filtered, then the filtrate ispreferably concentrated under vacuum. The xanthate of formula (II) maysubsequently be used in the process in accordance with the presentinvention without additional purification.

According to a first embodiment of the invention, the xanthate offormula (II) is O-1,2-dimethylpropyl S-methoxycarbonylmethyl xanthate(XA1) or O-1,2-dimethylpropyl S-(1-methoxycarbonyl)ethyl xanthate (XA2).

According to a second embodiment of the invention, the xanthate offormula (II) is as defined in the invention [i.e. with R¹, R², R³, R⁴,Y, X and R⁵ as defined in the invention], excluding the xanthates of thefirst embodiment above.

Step 1) of preparing the monoadduct of formula (IV) of the process inaccordance with the invention may be carried out without solvent, inwater or in an organic solvent. It is preferably carried out in anorganic solvent or in water, and even more preferentially in an organicsolvent. The organic solvent of use during this step 1) is thuspreferably chosen from toluene, tetrahydrofuran (THF), ethyl acetate and1,4-dioxane. Among such organic solvents, toluene is particularlypreferred.

For the purposes of the present invention, radical initiator is intendedto mean a chemical entity capable of forming free radicals, that is tosay a chemical entity having one or more unpaired electrons in its outershell.

According to the process in accordance with the invention, the radicalinitiator used during step 1) is preferably chosen from organicperoxides, azo derivatives, redox couples that generate radicals andredox systems.

Among the organic peroxides, mention may in particular be made ofdilauroyl peroxide (LPO), t-butyl peroxyacetate, t-butyl peroxybenzoate,t-butyl peroxyoctoate, t-butyl peroxydodecanoate, t-butylperoxyisobutyrate, t-amyl peroxypivalate, t-butyl peroxypivalate,diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumylperoxide, dibenzoyl peroxide, potassium peroxydisulfate, sodiumperoxydisulfate and ammonium peroxydisulfate. Among these organicperoxides, LPO is particularly preferred.

Among the azo derivatives, mention may in particular be made of2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-cyano-2-butane),dimethyl-2,2′-azobisdimethylisobutyrate, 4,4′-azobis-(4-cyanopentanoicacid), 1,1′-azobis(cyclohexanecarbonitrile),2-(t-butylazo)-2-cyanopropane,2,2′-azobis[2-methyl-N(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propanamide, 2,2′-azobis[2-methyl-N-hydroxyethyl] propanamide,2,2′-azobis([N,N′-dimethyleneisobutyramidine) dihydrochloride,2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′-azobis(N,N′-dimethylene isobutyramine), 2,2′-azobis(2-methyl-N-[1,bis(hydroxymethyl)-2-hydroxyethyl]propionamide),2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)propionamide],2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],2,2′-azobis(isobutyramide) dihydrate,2,2′-azobis(2,2,4-trimethylpentane) and 2,2′-azobis(2-methylpropane).

The redox systems are for example chosen from systems comprisingcombinations such as:

-   -   mixtures of hydrogen peroxide, an alkyl, a perester, a        percarbonate and similar compounds and an iron salt, a titanium        salt, zinc formaldehyde sulfoxylate or sodium formaldehyde        sulfoxylate, and a reducing sugar,    -   mixtures of an alkali metal or ammonium persulfate, perborate or        perchlorate and an alkali metal bisulfite, such as sodium        metabisulfite, and a reducing sugar, and    -   mixtures of an alkali metal persulfate with an arylphosphinic        acid, such as benzenephosphonic acid and other similar        compounds, and a reducing sugar.

Among such redox systems, the combination of ammonium persulfate andsodium formaldehyde sulfoxylate is most particularly preferred.

Moreover, during step 1), the radical initiator may be added to thereaction medium all at once or in several goes, that is to sayportionwise. According to a preferred embodiment form of the process ofthe invention, the radical initiator is added to the reaction mediumportionwise.

According to a first embodiment of the invention, the monoadduct offormula (IV) as obtained at the end of step 1) is chosen fromO-1,2-dimethylpropylS-(1-(dimethylphosphoryl)-3-(methoxycarbonyl))propyl xanthate (XA1VP),O-1,2-dimethylpropylS-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate (XA2AP),O-1,2-dimethylpropylS-(1-(diethylphosphoryl)-4-(methoxycarbonyl))but-2-yl xanthate (XA3AP),O-1,2-dimethylpropyl S-2-(methoxycarbonyl)non-4-yl xanthate (XA4H),O-1,2-dimethylpropyl S-1-(methoxycarbonyl)oct-3-yl xanthate (XA5H),methyl-5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)dodecanoate(XA6DF), the monoadduct of example 7 below (XA7MAL) and methyl5,5,6,6,7,7,8,8,8-nonafluoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)octanoate(XA8HF).

According to a second embodiment of the invention, the monoadduct offormula (IV) is as defined in the invention [i.e. with R¹, R², R³, R⁴,Y, X, R⁵, Z³, W, T, e, L and m as defined in the invention], excludingthe monoadducts of the first embodiment above.

The monomers of formula (III) are preferably chosen from compounds whichare monomers that are only slightly, or not at all, polymerizable underthe temperature and pressure conditions used during step 1) of theprocess in accordance with the invention, that is to say which lead to amonoadduct of formula (IV) without a notable presence of diadduct,triadduct, etc. Among such monomers of formula (III), mention may inparticular be made of alkenes and allylic compounds.

Among the alkenes of use as monomer of formula (III), mention may inparticular be made of ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,perfluorohexylethylene and perfluorooctylethylene.

Among allylic compounds of use as monomer of formula (III), mention mayin particular be made of allylic alcohol, N-allyl benzamide, ethylN-allyl carbamate, tert-butyl N-allyl carbamate,2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,2-allyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione, allylboronic acid,diethyl allylphosphonate, allyl phosphonic dichloride, dimethylallylphosphonate, allyl cyanide, allyl isothiocyanate, allyl glycidylether, allyl benzyl ether, allyl phenyl ether, allyl butyl ether, allylethyl ether, allyl methylsulfone, allyl phenylsulfone, allyl chloride,allyl bromide and allyl fluoride.

The monomers of formula (III) may also be chosen from polymerizablecompounds, in particular from styrene vinyl compounds, acrylic acid andacrylates, and acrylamide and derivatives thereof. In this case thesynthesis is not selective but predominantly obtaining the monoadductmay be promoted by using a smaller amount of monomer of formula (III)than the amount of xanthate of formula (II) so as to limit as far aspossible the risk of polymerization of the monomer of formula (III).Moreover, the monoadduct of formula (IV) may be isolated by conventionaltechniques that are within the grasp of those skilled in the art.

Among the vinyl compounds of use as monomer of formula (III), mentionmay in particular be made of dimethyl vinylphosphonate, diethylvinylphosphonate, vinylphosphonic acid, N-vinyl monomers such asN-vinylpyrrolidone, N-vinylcaprolactam and N-methyl-N-vinylacetamide,vinylsulfones such as methyl vinylsulfone and phenyl vinylsulfone,vinylsilanes such as vinyltrimethylsilane and vinyltrimethoxysilane, andvinyl esters, such as vinyl acetate, vinyl pivalate, vinyl butyrate,vinyl valerate, vinyl propionate, vinyl benzoate, vinyl neodecanoate andvinyl trifluoroacetate.

Among the styrene compounds of use as monomer of formula (III), mentionmay in particular be made of styrene, vinylbenzoic acid,3-chlorostyrene, 2-methylstyrene, p-t-butylstyrene, p-methoxystyrene,p-methylstyrene, p-chloromethylstyrene and vinylphenylboronic acid.

Among the acrylates, mention may in particular be made of methylacrylate, n-butyl acrylate, t-butyl acrylate and 2-hydroxyethylacrylate.

Among the acrylamide derivatives, mention may in particular be made ofN-isopropylacrylamide, N,N-dimethylacrylamide, N-t-butylacrylamide andN-octylacrylamide.

The monomers of formula (III) are generally commercially available. Whenthey are not commercially available, they may be readily obtained bysynthesis routes that are well known to those skilled in the art.

Step 1) of the process in accordance with the invention is generallycarried out at a temperature varying from approximately 10 to 140° C.,and preferably from approximately 40 to 110° C., and even morepreferentially between approximately 65 and 90° C.

The duration of said step 1) generally varies from approximately 3 to 48hours, and even more preferentially from approximately 4 to 24 hours.

According to a particular and preferred embodiment form of theinvention, the monoadduct of formula (IV) obtained at the end of step 1)is purified, for example by silica gel chromatography, before being usedin the second step of thermolysis.

Step 2) of thermolysis of the process according to the present inventionmay be carried out with or without solvent. According to a preferredembodiment form of the invention, the step of thermolysis is carried outwithout solvent. The thermolysis temperature is generally between 40 and210° C., preferably between 100 and 200° C. and more particularlybetween 160 and 190° C.

The step of thermolysis is generally carried out at a temperaturesufficient to decompose the monoadduct of formula (IV).

In the present invention, the expression “thermolysis” means a thermaldecomposition. This is a chemical decomposition reaction caused by heat.In the present case, the action of the heat leads to the decompositionof the monoadduct of formula (IV), enabling the formation of thethiolactone of formula (I).

In other words, step 2) of the process of the invention does not employreagents other than the monoadduct of formula (IV) resulting from step1). Only the action of heat makes it possible to obtain the thiolactonesof formula (I).

Surprisingly, the monoadduct of formula (IV) obtained in step 1) has asuitable chemical structure, especially in terms of the definition ofthe groups R¹, R², R³, R⁴, R⁵, L (if m=1), Y, X, W, T (if e=1) and Z³,to enable the formation of a substituted thiolactone of formula (I) bythermolysis. In other words, cyclization to give thiolactone (I) isfavoured.

When the step of thermolysis is carried out in a solvent, then saidsolvent is preferably chosen from high boiling point solvents (that isto say solvents having a boiling point greater than or equal to thethermolysis temperature), such as, for example, 1,2-dichlorobenzene.

Moreover, the step of thermolysis may be carried out at atmosphericpressure or under vacuum, especially in the latter case, to eliminatethe volatile by-products which may have formed during the reaction.

According to a particular embodiment, the step of thermolysis is carriedout in a closed container (e.g. Schlenk tube) and preferably undervacuum.

According to a particular and preferred embodiment form of theinvention, the step of thermolysis is carried out without solvent andunder vacuum.

At the end of step 2) of thermolysis, the thiolactone of formula (I) ispreferably purified, for example by silica column chromatography.

Some of the substituted thiolactones of formula (I) that are directlyobtained by carrying out the preparation process in accordance with thefirst subject of the invention are novel per se and thus constitute thesecond subject of the invention.

Therefore, another subject of the present invention is the substitutedthiolactones of the following formula (I′):

wherein:

A′¹, A′², Y′, Z^(1′), L′, m′, T′ and e′ may respectively assume the samemeanings as those defined above for A¹, A², Y, Z¹, L, m, T and e for thethiolactones of formula (I), with the proviso that:

-   -   when e′=0 and W′=H and m′=0 and Y′=hydrogen, then Z^(1′) is        other than a hydrogen atom, than a linear alkyl chain or than a        phenyl ring; and    -   when e′=0 and W′=H and m′=0 and Y′ is a substituent having a        nitrogen atom directly bonded to the thiolactone ring, then        Z^(1′) is other than a hydrogen atom,

in so far as such thiolactones are described in the article by Espeel P.et al., European Polymer Journal, 2015, 62, 247-272.

Among the above substituted thiolactones of formula (I′), mention mayespecially be made of:

-   dimethyl 5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1);-   diethyl (4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate    (TL2);-   diethyl (5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3);-   3-methyl-5-pentyl-dihydrothiophen-2(3H)-one (TL4);-   5-pentyl-dihydrothiophen-2(3H)-one (TL5);-   3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6);-   3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione    (TL7);-   3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8);-   (4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid (TL9);-   ((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid    (TL10);-   (5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid (TL11);-   3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one (TL12);-   5-(trimethoxysilyl)dihydrothiophen-2(3H)-one (TL13);-   tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate    (TL14);-   tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate (TL15);-   3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one (TL16);-   5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one (TL17);-   3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one    (TL18);-   (5-oxo-tetrahydrothiophen-2-yl)phosphonic acid (TL19);-   5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one    (TL20);-   5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL21);-   5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL22);-   dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one    (TL23);-   5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL24);-   5-(9-bromononyl)3-methyldihydrothiophen-2(3H)-one (TL25);-   5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL26),    and-   5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL27).

The substituted thiolactones of formula (I) that are able to be obtainedby carrying out the process in accordance with the present invention andin particular the thiolactones of formula (I′) in accordance with thesecond subject of the present invention may advantageously be used forthe synthesis of polymers or for surface functionalization or polymerfunctionalization.

Thus, a third subject of the present invention is also the use of atleast one substituted thiolactone of formula (I) obtained according tothe process as defined according to the first subject of the invention,in particular of at least one substituted thiolactone of formula (I′),for the synthesis of polymers or for the functionalization of planarsurfaces of metal, glass or ceramic type, particles or polymers.

Regarding the preparation of polymers, the thiolactones of formula (I)and in particular of formula (I′) may be used in a polymerizationreaction comprising at least one step of reacting a thiolactone offormula (I), in particular of formula (I′), with a nucleophiliccompound, making it possible to open the thiolactone ring and to obtaina thiol which may subsequently be used in an addition or condensationpolymerization process with, for example, a monomer of diacrylate typesuch as described in the reference by Lei Yu et al, Polym. Chem., 2015,6, 1527-1532.

Regarding the surface functionalization or polymer functionalization, itis thus possible:

-   -   according to a first embodiment form to graft substituted        thiolactones of formula (I) (respectively of formula (I′)) to a        solid surface or to a polymer in the liquid state, said surface        or said polymer comprising chemical functions able to react with        the group Z¹ or Y (respectively Z^(1′) or Y′) of the        thiolactones of formula (I), respectively (I′), in order to form        a covalent bond, or strong interactions of hydrogen bond type.        By way of example, it is thus possible to graft a thiolactone        comprising a phosphonate group, such as the phosphonic acid        group of the thiolactone TL8 as group Z¹, to a metal surface.        According to this first embodiment form, after        functionalization, the integrity of the thiolactone ring is        preserved.    -   according to a second embodiment form to graft the substituted        thiolactone by opening the thiolactone ring on a solid surface        or on a polymer in the liquid state and reacting with any        substance that reacts with thiols, such as alkyl halides or        acrylates for example.

Depending on the nature of the groups Y or Z¹ (respectively Y′ andZ^(1′)), it thus becomes possible to provide a material or a polymerwith the properties corresponding to the type of groups Y or Z¹(respectively Y′ or Z^(1′)) grafted, for example release properties whenthe groups Y or Z¹ (respectively Y′ or Z^(1′)) are perfluorinatedgroups. It is also possible to introduce an additional function when thethiol obtained by opening the thiolactone is reacted with a functionalcompound that reacts with thiols.

The present invention is illustrated by the following embodimentexamples, to which, however, it is not limited.

EXAMPLES Example 1: Synthesis of dimethyl5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1) According to the Processin Accordance with the Invention

In this example the thiolactone of the following formula was prepared(TL1):

1) First Step: Preparation of O-1,2-dimethylpropylS-methoxycarbonylmethyl xanthate (Xanthate of formula (II); (XA1))

1.1) Sub-Step 1: Preparation of potassiumO-(1,2-dimethylpropyl)xanthogenate (XA0)

100 g (1.13 mol) of 3-methylbutan-2-ol (Alfa Aesar), 63.65 g ofpotassium hydroxide (KOH, Sigma-Aldrich) and carbon disulfide (CS₂,Sigma-Aldrich) were suspended in 500 ml of tetrahydrofuran (THF,Sigma-Aldrich) at room temperature for 24 hours.

After total dissolution of the KOH, the yellow emulsion was concentratedunder reduced pressure then triturated with pentane (Sigma-Aldrich) andfinally filtered to obtain 185 g of the expected product XA0 in the formof a yellow solid (185 g, yield 80%).

¹H NMR (300.13 MHz, D₂O, 298K) δ 5.31 (p, ³J_(H,H)=6.4 Hz, 1H,(CH₃)₂CHCH(O)CH₃); 2.07-1.84 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.27 (d,³J_(H,H)=6.4 Hz, 3H, (CH₃)₂CHCH(O)CH ₃); 0.96 (d, ³J_(H,H)=6.9 Hz, 6H,(CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, D₂O, 298K) δ 232.6 (C═S); 86.3((CH₃)₂CHCH(O)CH₃); 32.8 ((CH₃)₂ CHCH(O)CH₃); 17.7 ((CH₃)₂CHCH(O)CH₃);17.6 ((CH₃)₂CHCH(O)CH₃); 15.8 ((CH₃)₂CHCH(O)CH₃) ppm.

1.2) Sub-Step 2: Preparation of O-1,2-dimethylpropylS-methoxycarbonylmethyl xanthate (XA1)

0.21 mol (32.12 g) of methyl 2-bromoacetate (Sigma-Aldrich) was added toa suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above inthe preceding step 1.1) in 200 ml of acetone (Sigma-Aldrich), in an icebath. Once the addition had ended, the reaction medium was stirred atroom temperature for 3 hours then filtered. The filtrate wasconcentrated under vacuum in order to obtain the expected product XA1 inthe form of a yellow oil (42 g, yield 89%) which will be used in thefollowing step without purification.

2) Second Step: Preparation of O-1,2-dimethylpropylS-(1-(dimethylphosphoryl)-3-(methoxycarbonyl))propyl xanthate (XA1VP:Monoadduct of Formula (IV))

14.2 g (60 mmol) of the xanthate XA1 obtained above in the precedingstep, 2.72 g (20 mmol) of dimethyl vinylphosphonate and 1.2 g (3 mmol)of dilauroyl peroxide (LPO: radical initiator) were mixed in a Schlenktube. The mixture was subsequently degassed by 3 operations of freezingunder vacuum. After 5 hours of heating at a temperature of 90° C., thecrude reaction product was purified by silica chromatography (eluentethyl acetate/petroleum ether (95:5, v:v) to recover the unreactedxanthate XA1, and with an eluent formed from a mixture of ethylacetate/dichloromethane (1:4, v:v) to recover the monoadduct XA1VP (3.13g, yield 42%, yellow oil).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.53-5.33 (m, 1H, (CH₃)₂CHCH(O)CH₃);4.31-4.11 (m, 1H, CHP); 3.75-3.65 (m, 6H, O═P(OCH ₃)₂); 3.59 (s, 3H,CO₂CH ₃); 2.56-2.44 (m, 2H, CH₂CH ₂CO₂CH₃); 2.43-1.87 (m, 2H, CH₂CH₂CO₂CH₃); 2.02-1.87 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.25-1.21 (m, 3H,(CH₃)₂CHCH(O)CH ₃); 0.89-0.86 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 211.8-211.5 (C═S); 175.7(CO₂CH₃); 87.3; 87.2 ((CH₃)₂CHCH(O)CH₃); 53.9-53.4 (O═P(OCH₃)₂); 51.7(CO₂ CH₃); 44.6-42.5 (CHP); 32.7 ((CH₃)₂ CHCH(O)CH₃); 31.0-30.8 (CH₂CH₂CO₂CH₃); 25.1-24.9 (CH₂CH₂CO₂CH₃); 18.0-17.8 ((CH₃)₂CHCH(O)CH₃);15.7; 15.6 ((CH₃)₂CHCH(O)CH₃).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 26.3; 26.2 ppm.

IR: 1738.5 cm⁻¹ (C═O), 1035.1 cm⁻¹ (C═S).

Molar mass: IC(CH₄), MH⁺:

Found: 373.0916 g/mol

Calculated: 373.0908 g/mol.

3) Third Step: Preparation of dimethyl5-oxo-tetrahydrothiophen-2-ylphosphonate (TL1)

3.70 g (10 mmol) of XA1VP obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 15 minutes. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL1 thus obtainedin the form of a colourless oil (1.2 g, yield 57%) was subsequentlypurified on a silica chromatography column (eluent ethylacetate/dichloromethane: 1:4 (v:v)).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 3.87-3.76 (m, 1H, CHP); 3.72-3.57 (m,6H, O═P(OCH₃)₂); 2.63-2.33 (m, 2H, CH₂CH ₂CHP); 2.32-2.17 (m, 2H, CH₂CH₂CHP).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 205.7-205.6 (C═O); 53.2-53.1(O═P(OCH₃)₂); 42.3-40.2 (CHP); 39.6-39.5 (CH₂CH₂CHP); 25.40-25.35 (CH₂CH₂CHP).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 25.7 ppm.

IR: 1713.9 cm⁻¹ (C═O).

Molar mass: IC(CH₄), MH⁺

Found: 211.0198 g/mol

Calculated: 211.0194 g/mol.

Example 2: Synthesis of diethyl(4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL2)According to the Process in Accordance with the Invention

1) First Step: Preparation of O-1,2-dimethylpropylS-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate(Monoadduct of Formula (IV): XA2AP)

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropylS-(1-methoxycarbonyl)ethyl xanthate (XA2)

0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was addedto a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained abovein the preceding step 1.1) of example 1, in 200 ml of acetone(Sigma-Aldrich), in an ice bath. Once the addition had ended, thereaction medium was stirred at room temperature for 3 hours thenfiltered. The filtrate was concentrated under vacuum in order to obtainthe expected product XA2 in the form of a yellow oil (43 g, yield 86%)which will be used in the following step without purification.

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.51 (p, ³J_(H,H)=6.3 Hz, 1H,(CH₃)₂CHCH(O)CH₃); 4.42-4.30 (m, 1H, CH(CH₃)CO₂CH₃); 3.73 (s, 3H, CO₂CH₃); 2.09-1.88 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.56-1.52 (m, ³J_(H,H)=7.4 Hz,3H, CH(CH ₃)CO₂CH₃); 1.29-1.25 (m, ³J_(H,H)=6.4 Hz, 3H, (CH₃)₂CHCH(O)CH₃); 1.02-0.91 (m, 6H, (CH ₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 211.4; 211.4 (C═S); 172.0(CO₂CH₃); 86.2-86.1 ((CH₃)₂CHCH(O)CH₃); 52.8 (CO₂ CH₃); 46.5(CH(CH₃)CO₂CH₃); 32.7 ((CH₃)₂ CHCH(O)CH₃); 18.2-17.8 ((CH₃)₂CHCH(O)CH₃);17.0-16.9 (CH(CH₃)CO₂CH₃); 15.8-15.7 ((CH₃)₂CHCH(O)CH₃) ppm.

IR: 1738.5 cm⁻¹ (C═O); 1046.2 cm⁻¹ (C═S)

1.2) Sub-Step 2: Preparation of O-1,2-dimethylpropylS-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate (XA2AP)

9.26 g (37 mmol) of the xanthate XA2 obtained above in step 1.1), 5.87 g(33 mmol) of diethyl allylphosphonate (DEAP, Alfa Aesar) and 2 g (5mmol) of LPO were dissolved in 5 ml of toluene (Sigma-Aldrich). Thesolution thus obtained was transferred to a Schlenk tube and degassed by3 successive operations of freezing under vacuum. After 18 hours ofheating at 90° C., 10.1 g of crude reaction product were obtained in theform of a yellow oil (yield 79%) which was purified by silicachromatography (eluent ethyl acetate/dichloromethane: 1:4, v:v).

12.7 g of XA2AP were thus obtained (yield 90%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.54-5.46 (m, 1H, (CH₃)₂CHCH(O)CH₃);4.15-4.02 (m, 4H, O═P(OCH ₂CH₃)₂); 4.02-3.89 (m, 1H, CHS); 3.62 (s, 3H,CO₂CH ₃); 2.75-1.63 (m, 6H, CH ₂P, (CH₃)₂CHCH(O)CH₃, CH ₂CHCO₂CH₃);1.32-1.23 (m, 9H, O═P(OCH₂CH ₃)₂, CH ₃CHCO₂CH₃); 1.17-1.14 (m, 3H,(CH₃)₂CHCH(O)CH ₃); 0.92-0.90 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 212.7-215.6 (C═S); 176.2-176.0(CO₂CH₃); 85.8-85.7 ((CH₃)₂CHCH(O)CH₃); 62.0-61.8 (O═P(OCH₂CH₃)₂); 51.8(CO₂ CH₃); 43.8-43.6 (CHS); 37.8-36.6 (CH ₂P); 37.3-37.1 ((CH₃)₂CHCH(O)CH₃); 33.4-31.1 (CH₂CH₂CO₂CH₃); 32.7 (CHCO₂CH₃); 18.3-17.9((CH₃)₂CHCH(O)CH₃); 18.3-17.8 (CH₃CHCO₂CH₃); 16.6-165 (O═P(OCH₂ CH₃)₂);15.9-15.8 ((CH₃)₂CHCH(O)CH₃).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 26.7 ppm.

IR: 1736.9 cm⁻¹ (C═O); 1043.6 cm⁻¹ (C═S)

Molar mass: IC(CH₄), MH⁺

Found: 429.1533 g/mol

Calculated: 429.1534 g/mol.

2) Second Step: Preparation of diethyl(4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL2)

4.28 g (10 mmol) of XA2AP obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 15 minutes. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL2 thus obtainedin the form of a colourless oil (2.4 g, yield 90%) was subsequentlypurified on a silica chromatography column (eluent ethylacetate/dichloromethane: 1:4 (v:v)).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 4.18-4.05 (m, 4H, O═P(OCH ₂CH₃)₂);4.05-3.90 (m, 1H, CHCH₂P); 2.77-2.29 (m, 2H, CH ₂CH(CH₃)); 2.28-2.07 (m,2H, CHCH ₂P); 1.62-1.20 (m, 1H, CHCH₂P); 1.35-1.29 (m, 6H, O═P(OCH₂CH₃)₂); 1.19-1.14 (m, 3H, CH₂CH(CH ₃)).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 210.0-209.0 (C═O); 62.2-62.1(O═P(OCH₂CH₃)₂); 48.7-45.4 (CHCH₂P); 42.6-42.4 (CH₂CH(CH₃)); 41.0-40.9(CH₂ CH(CH₃)); 34.2-31.7 (CHCH₂P); 16.6-16.5 (O═P(OCH₂ CH₃)₂); 15.2-14.3(CH₂CH(CH₃)).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 26.40, 26.36 ppm.

IR: 1700.5 cm⁻¹ (C═O); 1245.7 cm⁻¹ (P═O); 1025.4 cm⁻¹ (P—O)

Molar mass: IC(CH₄), MH⁺

Found: 267.0826 g/mol

Calculated: 267.0820 g/mol.

Example 3: Synthesis of diethyl(5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3) According to theProcess in Accordance with the Invention

1) First Step: Preparation of O-1,2-dimethylpropylS-(1-(diethylphosphoryl)-4-(methoxycarbonyl))but-2-yl xanthate(Monoadduct of Formula (IV): XA3AP)

The monoadduct XA3AP was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above instep 1) of example 1, 5.88 g (33 mmol) of DEAP (Sigma-Aldrich) and 2 g(5 mmol) of LPO.

12.31 g of XA3AP were thus obtained (yield 90%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.49-5.39 (m, 1H, (CH₃)₂CHCH(O)CH₃);4.09-3.96 (m, 4H, O═P(OCH ₂CH₃)₂); 3.96-3.87 (m, 1H, CHS); 3.55 (s, 3H,CO₂CH ₃); 2.48-1.84 (m, 7H, CH ₂P, (CH₃)₂CHCH(O)CH₃, CH ₂CH ₂CO₂CH₃);1.26-1.20 (m, 6H, O═P(OCH₂CH ₃)₂); 1.20-1.17 (m, 3H, (CH₃)₂CHCH(O)CH ₃);0.86-0.83 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 212.2 (C═S); 172.8 (CO₂CH₃); 85.6((CH₃)₂CHCH(O)CH₃); 61.9-61.7 (O═P(OCH₂CH₃)₂); 51.5 (CO₂ CH₃); 44.5(CHS); 32.5 ((CH₃)₂ CHCH(O)CH₃); 32.5-30.5 (CH ₂P); 31.2-31.1 (CH₂CH₂CO₂CH₃); 29.1-28.7 (CH₂CH₂CO₂CH₃); 18.1-17.8 ((CH₃)₂CHCH(O)CH₃);16.4-16.3 (O═P(OCH₂ CH₃)₂); 15.6 ((CH₃)₂CHCH(O)CH₃).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 26.53; 26.51 ppm.

IR: 1738.8 cm⁻¹ (C═O); 1044.9 cm⁻¹ (C═S)

Molar mass: IC(CH₄), MH⁺

Found: 415.1390 g/mol

Calculated: 415.1378 g/mol.

2) Second Step: Preparation of diethyl(5-oxo-tetrahydrothiophen-2-yl)methylphosphonate (TL3)

The thiolactone TL3 was prepared according to the same procedure as thatused above in example 2, step 2) for the preparation of the thiolactoneTL2, but using 4.14 g (10 mmol) of the monoadduct XA3AP prepared abovein the preceding step instead of the monoadduct XA2AP.

2.3 g of TL3 were thus obtained in the form of a colourless oil (yield91%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 4.15-4.00 (m, 5H, CHCH₂P, O═P(OCH₂CH₃)₂); 2.63-2.45 (m, 3H, CH₂CH ₂CO, CH ₂CH₂CO); 2.29-2.08 (m, 2H, CHCH₂P); 2.05-1.89 (m, 1H, CH₂CH ₂CO); 1.32-1.25 (m, 6H, O═P(OCH₂CH ₃)₂).

¹³C{¹H} ¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 207.4 (C═O); 62.1-62.0(O═P(OCH₂CH₃)₂); 44.44-44.39 (CHCH₂P); 41.8 (CH₂ CH₂CO); 33.7-31.8(CHCH₂P); 33.4-33.3 (CH₂CH₂CO); 16.5-16.4 (O═P(OCH₂ CH₃)₂).

³¹P NMR{¹H} (121.49 MHz, CDCl₃, 298K) δ 26.2 ppm.

IR: 1704.4 cm⁻¹ (C═O); 1250.5 cm⁻¹ (P═O); 1025.2 cm⁻¹ (P—O)

Molar mass: IC(CH₄), MH⁺

Found: 253.0667 g/mol

Calculated: 253.0663 g/mol.

Example 4: Synthesis of 3-methyl-5-pentyl-dihydrothiophen-2(3H)-one(TL4) According to the Process in Accordance with the Invention

1) First Step: Preparation of O-1,2-dimethylpropylS-2-(methoxycarbonyl)non-4-yl xanthate (Monoadduct of Formula (IV):XA4H)

The monoadduct XA4H was prepared according to the same procedure as thatused above in step 1.2) of example 2 for the preparation of themonoadduct XA2AP, but using 9.26 g (37 mmol) of the xanthate XA2prepared in step 1.1) of example 2, 3.24 g (33 mmol) of 1-heptene(Sigma-Aldrich) and 2 g (5 mmol) of LPO.

10.7 g of XA4H were thus obtained (yellow oil; eluent ethylacetate/petroleum ether (95:5; v:v), in the form of a racemate (yield92%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.59-5.46 (m, 1H, (CH₃)₂CHCH(O)CH₃);3.78-3.64 (m, 1H, SCHCH₂CH(CH₃)CO₂CH₃); 3.64-3.61 (m, 3H, CO₂CH ₃);2.73-2.54 (m, 1H, SCHCH₂CH(CH₃)CO₂CH₃); 2.13-1.87 (m, 2H, SCHCH₂CH(CH₃)CO₂CH₃); 1.75-1.47 (m, 3H, (CH₃)₂CHCH(O)CH₃, CH ₂(CH₂)₃CH₃);1.47-1.31 (m, 2H, CH₂CH ₂(CH₂)₂CH₃); 1.31-1.18 (m, 7H, CH(CH ₃)CO₂CH₃,(CH₂)₂(CH ₂)₂CH₃); 1.18-1.09 (m, 3H, (CH₃)₂CHCH(O)CH ₃); 0.97-0.87 (m,6H, (CH ₃)₂CHCH(O)CH₃); 0.87-0.79 (m, 3H, (CH₂)₄CH ₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 213.8-213.7 (C═S); 176.3-176.3(CO₂CH₃); 85.2-85.0 ((CH₃)₂CHCH(O)CH₃); 51.6 (CO₂ CH₃); 49.1-48.6(SCHCH₂CH(CH₃)CO₂CH₃); 38.1-37.5 (SCHCH₂CH(CH₃)CO₂CH₃); 37.2-37.1(SCHCH₂ CH(CH₃)CO₂CH₃); 35.2-34.7 (CH₂(CH₂)₃CH₃); 32.7 ((CH₃)₂CHCH(O)CH₃); 31.6 ((CH₂)₂ CH₂CH₂CH₃); 26.3-26.2 (CH₂ CH₂(CH₂)₂CH₃); 22.4((CH₂)₃ CH₂CH₃); 18.1-17.0 ((CH₃)₂CHCH(O)CH₃); 17.9-17.8(CH(CH₃)CO₂CH₃); 15.71-15.69 ((CH₃)₂CHCH(O)CH₃); 13.9 (SCH(CH₂)₄ CH₃)ppm.

IR: 1738.5 cm⁻¹ (C═O); 1047.2 cm⁻¹ (C═S).

Molar mass: IC(CH₄), MH⁺

Found: 349.1861 g/mol

Calculated: 349.1871 g/mol.

2) Second Step: Preparation of3-methyl-5-pentyl-dihydrothiophen-2(3H)-one (TL4)

The thiolactone TL4 was prepared according to the same procedure as thatused above in example 2, step 2) for the preparation of the thiolactoneTL2, but using 3.48 g (10 mmol) of the monoadduct XA4H prepared above inthe preceding step instead of the monoadduct XA2AP.

1.73 g of thiolactone TL4 were thus obtained (yield 93%) in the form ofa colourless liquid (eluent: ethyl acetate/petroleum ether: 9:1; v:v).

¹H NMR (300 MHz, CDCl₃, 298K) δ 3.79-3.64 (m, 1H, SCHCH₂CH); 2.76-2.46(m, 2H, SCHCH ₂CH); 2.20-1.97 (m, 1H, SCHCH₂CH); 1.83-1.62 (m, 2H, CH₂CH₂(CH₂)₂CH₃); 1.55-1.35 (m, 2H, CH ₂(CH₂)₃CH₃); 1.35-1.21 (m, 4H,(H₂)₂(CH ₂)₂CH₃); 1.20-1.13 (m, 3H, CHCH ₃); 0.92-0.84 (m, 3H, (CH₂)₄CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 211.2-210.0 (C═O); 48.92-47.89(SCHCH₂CH); 47.5-456 (SCHCH₂ CH); 415-39.7 (SCHCH₂CH); 36.8-36.5(CH₂(CH₂)₃CH₃); 31.7-31.6 ((CH₂)₂ CH₂CH₂CH₃); 28.2-28.0 (CH₂CH₂(CH₂)₂CH₃); 22.60-22.56 ((CH₂)₃ CH₂CH₃); 15.5-14.6 (CHCH₃); 14.1((CH₂)₄ CH₃) ppm.

IR: 1700.9 cm⁻¹ (C═O).

Molar mass: IE

Found: 186.1075 g/mol

Calculated: 186.1078 g/mol.

Example 5: Synthesis of 5-pentyl-dihydrothiophen-2(3H)-one (TL5)According to the Process in Accordance with the Invention

1) First Step: Preparation of O-1,2-dimethylpropylS-1-(methoxycarbonyl)oct-3-yl xanthate (Monoadduct of Formula (IV):XA5H)

The monoadduct XA5H was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above in step1.2) of example 1, 3.24 g (33 mmol) of 1-heptene and 2 g (5 mmol) ofLPO.

10 g of thiolactone XA5H were thus obtained in the form of a yellow oil(eluent: ethyl acetate/petroleum ether: 95:5; v:v) in the form of aracemate (yield 90%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.53 (p, ³J_(H,H)=6.3 Hz, 1H,(CH₃)₂CHCH(O)CH₃); 3.78-3.66 (m, 1H, SCHCH₂CH₂CO₂CH₃); 3.64 (s, 3H,CO₂CH ₃); 2.49-2.36 (m, 2H, SCHCH₂CH ₂CO₂CH₃); 2.12-1.94 (m, 2H, CH₂(CH₂)₃CH₃); 1.93-1.77 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.69-1.52 (m, 2H,SCHCH₂CH ₂CO₂CH₃); 1.52-1.33 (m, 2H, CH₂CH ₂(CH₂)₂CH₃); 1.33-1.16 (m,7H, (CH₂)₂(CH ₂)₂CH₃; (CH₃)₂CHCH(O)CH ₃); 0.93 (d, J=6.8 Hz, 6H, (CH₃)₂CHCH(O)CH₃); 0.89-0.79 (m, 3H, (CH₂)₄CH ₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 214.0-213.9 (C═S); 173.5-173.5(CO₂CH₃); 85.4-85.4 ((CH₃)₂CHCH(O)CH₃); 51.7 (CO₂ CH₃); 50.3-50.2(SCHCH₂CH₂CO₂CH₃); 34.6-34.3 (CH₂(CH₂)₃CH₃); 32.8 ((CH₃)₂ CHCH(O)CH₃);31.7 ((CH₂)₂ CH₂CH₂CH₃); 31.5-31.4 (SCHCH₂CH₂CO₂CH₃); 29.7-29.3 (SCHCH₂CH₂CO₂CH₃); 26.6-26.5 (CH₂ CH₂(CH₂)₂CH₃); 22.6 ((CH₂)₃ CH₂CH₃);18.3-18.0 ((CH₃)₂CHCH(O)CH₃); 15.8 ((CH₃)₂CHCH(O)CH₃); 14.1 ((CH₂)₄ CH₃)ppm.

IR: 1740.9 cm⁻¹ (C═O); 1048.6 cm⁻¹ (C═S).

Molar mass: IC(CH₄), MH⁺

Found: 335.1701 g/mol

Calculated: 335.1715 g/mol

2) Second Step: Preparation of 5-pentyl-dihydrothiophen-2(3H)-one (TL5)

The thiolactone TL5 was prepared according to the same procedure as thatused above in example 2, step 2) for the preparation of the thiolactoneTL2, but using 3.34 g (10 mmol) of the monoadduct XA5H prepared above inthe preceding step instead of the monoadduct XA2AP.

1.55 g of TL5 were thus obtained in the form of a colourless liquid(eluent: ethyl acetate/petroleum ether: 9:1; v:v) (yield 90%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 3.82 (tt, ³J_(H,H)=8.5; 5.8 Hz, 1H,SCHCH₂CH₂); 2.66-2.44 (m, 2H, SCHCH₂CH ₂); 2.43-1.79 (m, 2H, SCHCH₂CH₂); 1.79-1.62 (m, 2H, CH₂CH ₂(CH₂)₂CH₃); 1.47-1.33 (m, 2H, CH₂(CH₂)₃CH₃); 1.32-1.19 (m, 4H, (CH₂)₂(CH ₂)₂CH₃); 0.86 (t, ³J_(H,H)=7.0Hz, 3H, (CH₂)₄CH ₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 208.6 (C═O); 51.4 (SCHCH₂CH₂);42.1 (SCHCH₂ CH₂); 36.5 (CH₂(CH₂)₃CH₃); 32.3 ((CH₂)₂CH₂ CH₂CH₃); 31.5(SCHCH₂CH₂); 28.0 (CH₂ CH₂(CH₂)₂CH₃); 22.5 ((CH₂)₃ CH₂CH₃); 14.0 ((CH₂)₄CH₃) ppm.

IR: 1704.6 cm⁻¹ (C═O)

Mass: IE

Found: 172.0910 g/mol

Calculated: 172.0922 g/mol.

Example 6: Synthesis of3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6) According tothe Process in Accordance with the Invention

1) First Step: Preparation of Methyl5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafiuoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)dodecanoate(Monoadduct of Formula (IV): XA6DF)

The monoadduct XA6DF was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 3.09 g (1.23×10⁻² mol) of xanthate XA2 as prepared above instep 1.1) of example 2, 5 g (1.12×10⁻² mol) of1H,1H,2H-perfluoro-1-decene (Aldrich), 0.67 g of LPO, and a reactionsolvent composed of 4 ml of toluene and 3 ml of trifluorotoluene.

The monoadduct XA6DF obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 9:1,v:v).

3.2 g of XA6DF were thus obtained (yield 41%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 5.58-5.47 (s, 1H,(CH₃)₂CHCH(O)CH₃); 4.87-4.67 (m, 1H, SCHCH₂CH(CH₃)); 3.70-3.68 (m, 3H,CO₂CH ₃); 2.92-2.68 (1H, m, SCHCH₂CH(CH₃)); 2.14-1.92 (m, 1H,(CH₃)₂CHCH(O)CH₃); 1.58-1.53 (m, 2H, SCHCH ₂CH(CH₃)); 1.32-1.20 (m, 6H;(CH₃)₂CHCH(O)CH ₃ et SCHCH₂CH(CH ₃)); 0.97-0.93 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K): δ (ppm) 209.33 (C═S); 175.54(CO₂CH₃); 129.01-115.52 (CH(CF₂)₇ CF₃); 87.48 ((CH₃)₂CHCH(O)CH₃);52.71-51.79 (CO₂ CH₃); 46.50 (CH(CF₂)₃CF₃); 36.48 (SCHCH₂ CH(CH₃));32.71 ((CH₃)₂ CHCH(O)CH₃); 18.30-15.44 ((CH₃)₂CHCH(O)CH₃ et(SCHCH₂CH(CH₃)).

NMR ¹⁹F{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) −80.83(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₃)); −105.65-−116.25 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −118.87-−119.33 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −121.69-−121.91 (CH(CF₂—CF₂—CF ₂—CF ₂—CF₂—CF₂—CF₂—CF₃)); −122.72 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₂—CF₃)); −126.16(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₃)).

2) Second Step: Preparation of3-Methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one (TL6)

2 g (2.87 mmol) of XA6DF obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL6 thus obtainedin the form of a yellow oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).

0.8 g of TL6 were thus obtained in the form of a white powder (yield52%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 4.49-4.36 (m, 1H, CHCF₂);2.75-2.59 (m, 2H, C(O)CH(CH₃)CH ₂CH); 1.99-1.87 (q, 1H,C(O)CH(CH₃)CH₂CH); 1.26-1.23 (d, 3H, C(O)CH(CH ₃)).

NMR ¹⁹F{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) −81.03(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₃)); −112.13-−119.71 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −121.08 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −121.96 (CH(CF₂—CF₂—CF ₂—CF ₂—CF₂—CF₂—CF₂—CF₃)); −122.86 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₂—CF₃)); −126.29(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₃)).

Example 7: Synthesis of3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione(TL7) According to the Process in Accordance with the Invention

1) First Step: Preparation of XA7MAL (Monoadduct of Formula (IV))

The monoadduct XA7MAL was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 4.77 g (1.91×10⁻² mol) of the xanthate XA2 as prepared abovein step 1.1) of example 2, 3 g (1.73×10⁻² mol) of N-phenylmaleimide(Aldrich) and 1.03 g of LPO.

The monoadduct XA7MAL obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 7:3,v:v).

4.9 g of XA7MAL were thus obtained (yield 68%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 7.47-7.30 (m, 5H, N—C₆ H ₅);5.57-5.48 (s, 1H, (CH₃)₂CHCH(O)CH₃); 5.22-4.07 (m, 1H, SCH(CO)CH);3.76-3.66 (m, 3H, CO₂CH₃); 3.55-3.21 (m, 2H, SCH(CO)CH(CO)CH(CH₃));2.07-1.92 (1H, (CH₃)₂CHCH(O)CH₃); 1.56-1.39 (m, 3H, CH(CO)CH(CH ₃));1.39-1.26 (m, 3H, (CH₃)₂CHCH(O)CH ₃); 0.98-0.92 (m, 3H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K): δ (ppm) 209.77 (C═S);175.59-171.71 (C(O)NC(O) et CO₂CH₃); 131.38-126.36 (N—C ₆H₅); 87.27((CH₃)₂CHCH(O)CH₃); 52.42 CO₂ CH₃); 50.47-46.87 (SCH(CO)CH(CO)CH(CH₃));39.71-38.99 (SCH(CO)CH(CO)CH(CH₃)); 32.82 ((CH₃)₂ CHCH(O)CH₃);18.34-17.84 ((CH₃)₂CHCH(O)CH₃); 15.81-15.21 (SCH(CO)CH(CO)CH(CH₃)).

2) Second Step: Preparation of3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione(TL7)

1 g (2.36 mmol) of XA7MAL obtained above in the preceding step wasplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL7 thus obtainedin the form of a yellow oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).

0.4 g of TL7 were thus obtained (yield 65%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 7.55-7.30 (m, 5H, N—C₆ H ₅);4.86-4.75 (s, 1H, SCH(CO)CH); 3.46-3.44 (m, 1H, CH(CH₃)CHC(O));3.34-3.25 (m, 1H, C(O)CH(CH₃)); 1.49-1.47 (d, 3H, C(O)CH(CH ₃)).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K): δ (ppm) 205.25 (SC═O);174.5-173.49 (C(O)NC(O)); 129.21-126.39 (N—C ₆H₅) 49.54 (SCH(CO)); 49.03(C(O)CH(CH₃)); 46.81 (C(O)CH(CH₃)CH(CO); 18.41 (C(O)CH(CH₃)CH₂).

Example 8: Synthesis of3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8) According tothe Process in Accordance with the Invention

1) First Step: Preparation of methyl5,5,6,6,7,7,8,8,8-nonafluoro-2-methyl-4-((((3-méthylbutan-2-yl)oxy)carbonothioyl)thio)octanoate(Monoadduct of Formula (IV): XA8HF)

The monoadduct XA8HF was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 4.47 g (1.78×10⁻² mol) of the xanthate XA2 as prepared abovein step 1.1) of example 2, 4 g (1.62×10⁻² mol) of1H,1H,2H-perfluoro-1-hexene (Aldrich) and 0.969 g of LPO.

The monoadduct XA8HF obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 9:1,v:v).

3.73 g of XA8HF were thus obtained (yield 46%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 5.59-5.48 (s, 1H,(CH₃)₂CHCH(O)CH₃); 4.92-4.66 (m, 1H, SCHCH₂CH(CH₃)); 3.73-3.67 (m, 3H,CO₂CH ₃); 2.91-2.61 (1H, m, SCHCH₂CH(CH₃)); 2.16-1.88 (m, 1H,(CH₃)₂CHCH(O)CH₃); 1.60-1.52 (m, 2H, SCHCH ₂CH(CH₃)); 1.32-1.20 (m, 6H,(CH₃)₂CHCH(O)CH ₃ et SCHCH₂CH(CH ₃)); 0.96-0.92 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K): δ (ppm) 209.30 (C═S); 175.35(CO₂CH₃); 129.01-127.51 (CH(CF₂)₃ CF₃); 87.49 ((CH₃)₂CHCH(O)CH₃);52.70-51.91 (CO₂ CH₃); 46.48 CH(CF₂)₃CF₃); 36.46 (SCHCH₂ CH(CH₃)), 32.64((CH₃)₂ CHCH(O)CH₃); 18.32-14.08 ((CH₃)₂CHCH(O)CH₃ et (SCHCH₂CH(CH₃)).

NMR ¹⁹F{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) −80.80 (CH(CF₂—CF₂—CF₂—CF₃)), −105.96-−116.42 (CH(CF ₂—CF₂—CF₂—CF₃)), −119.86-−120.36 (CH(CF₂—CF₂—CF₂—CF₃)), −125.60-−126.30 (CH(CF₂—CF₂—CF ₂—CF₃)).

2) Second Step: Preparation of3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one (TL8)

2 g (4.03 mmol) of XA8HF obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL8 thus obtainedin the form of a colourless oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 5:95 (v:v)).

0.8 g of TL8 were thus obtained in the form of a white powder (yield52%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 4.49-4.36 (m, 1H, CHCF₂);2.75-2.59 (m, 2H, C(O)CH(CH₃)CH ₂CH); 1.99-1.87 (q, 1H,C(O)CH(CH₃)CH₂CH); 1.26-1.23 (d, 3H, C(O)CH(CH ₃)).

NMR ¹⁹F{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) −81.03(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₃)); −112.13-−119.71 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −121.08 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF₃)); −121.96 (CH(CF₂—CF₂—CF ₂—CF ₂—CF₂—CF₂—CF₂—CF₃)); −122.86 (CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₂—CF₃)); −126.29(CH(CF₂—CF₂—CF₂—CF₂—CF₂—CF₂—CF ₂—CF₃)).

Example 9: Functionalization of Polymers by a Thiolactone According tothe Invention 1) Example 9.1: Functionalization ofbis(3-aminopropyl)-poly(dimethylsiloxane) by TL4

The following were successively introduced into a 25 ml round-bottomedflask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol⁻¹, 500 mg,2×10⁻⁴ mol, Aldrich), TL4 (52.1 mg, 2.8×10⁻⁴ mol) and benzyl acrylate(45.4 mg, 2.8×10⁻⁴ mol, Aldrich). The reaction mixture was stirred for20 hours at 50° C. ¹H NMR analysis and MALDI-TOF analysis showed totalfunctionalization of the bis(3-aminopropyl)-poly(dimethylsiloxane).

2) Example 9.2: Functionalization of Methoxypolyethylene Glycol Amine byTL4

The following were successively introduced into a 25 ml round-bottomedflask: methoxypolyethylene glycol amine (2000 g·mol⁻¹, 200 mg, 1×10⁻⁴mol, Aldrich), TL4 (16.7 mg, 9×10⁻⁵ mol) and benzyl acrylate (14.6 mg,9×10⁻⁵ mol, Aldrich). The reaction mixture was stirred for 20 hours at60° C. ¹H NMR analysis and MALDI-TOF analysis showed totalfunctionalization of the methoxypolyethylene glycol amine.

3) Example 9.3: Functionalization ofbis(3-aminopropyl)-poly(dimethylsiloxane) by TL2

The following were successively introduced into a 25 ml round-bottomedflask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol⁻¹, 500 mg,2×10⁻⁴ mol, Aldrich), TL2 (74.5 mg, 2.8×10⁴ mol) and benzyl acrylate(45.4 mg, 2.8×10⁻⁴ mol, Aldrich). The reaction mixture was stirred for20 hours at 50° C. ¹H NMR analysis showed total functionalization of thebis(3-aminopropyl)-poly(dimethylsiloxane).

4) Example 9.4: Functionalization of methoxypolyethylene glycol amine byTL2

The following were successively introduced into a 25 ml round-bottomedflask: methoxypolyethylene glycol amine (2000 g·mol⁻¹, 200 mg, 1×10⁻⁴mol, Aldrich), TL2 (23.9 mg, 9×10⁻⁵ mol) and benzyl acrylate (14.6 mg,9×10⁻⁵ mol, Aldrich). The reaction mixture was stirred for 20 hours at60° C. ¹H NMR analysis showed total functionalization of themethoxypolyethylene glycol amine.

5) Example 9.5: Polymerization ofbis(3-aminopropyl)-poly(dimethylsiloxane) with TL2 and poly(ethyleneglycol) diacrylate

The following were successively introduced into a 25 ml round-bottomedflask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol⁻¹, 500 mg,2.0×10−4 mol, Aldrich), TL2 (74.5 mg, 2.8×10⁻⁴ mol) and poly(ethyleneglycol) diacrylate (575 g·mol⁻¹, 80.5 mg, 1.4×10−4 mol, Aldrich). Thereaction mixture was stirred for 20 hours at 50° C. H and ³¹P NMRanalysis showed total consumption of the monomers, and size exclusionchromatography confirmed the formation of the polymer. Mn_((PS))=8100g·mol⁻¹ Mw_((PS))=14 500 g·mol⁻¹.

Example 10: Synthesis ofdihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one(TL23) According to the Process in Accordance with the Invention

1) First Step: Preparation of the Monoadduct of Formula (IVa); XA23OD

The monoadduct XA23OD was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 4.77 g (1.90×10⁻² mol) of xanthate XA2 as prepared in step1.2) of example 2, 1 g (0.90×10⁻² mol) of 1,7-octadiene (Aldrich), 0.54g of LPO, and a reaction solvent composed of 2 ml of toluene.

The monoadduct XA23OD obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 95:5,v:v).

2.49 g of XA23OD were thus obtained (yield 45%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 5.47-5.46 (s, 2H,(CH₃)₂CHCH(O)CH₃); 3.77-3.78 (m, 2H, SCHCH₂CH(CH₃)); 3.66-3.64 (m, 6H,CO₂CH₃); 2.73-2.61 (2H, m, SCHCH₂CH(CH₃)); 2.15-1.91 (m, 4H,SCHCH₂CH(CH₃)); 1.73-1.49 (m, 6H, (CH₃)₂CHCH(O)CH₃ etSCH(CH₂CH₂)CH₂CH(CH₃)); 1.49-1.34 (m, 4H, SCH(CH₂CH₂)CH₂CH(CH₃));1.28-1.23 (d, 3H, SCHCH₂CH(CH₃)); 1.17-1.15 (d, 3H, (CH₃)₂CHCH(O)CH₃);0.94-0.92 (m, 6H, (CH₃)₂CHCH(O)CH₃).

2) Second Step: Preparation ofdihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one(TL23)

2.49 g (4.1 mmol) of XA23OD obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL9 thus obtainedin the form of a yellow oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 8:2 (v:v)).

0.877 g of TL23 were thus obtained in the form of a white powder (yield75%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS);2.75-2.43 (m, 2H, C(O)CH(CH₃)CH ₂CH); 2.20-1.99 (m, 2H, C(O)CH(CH₃)CH₂CH); 1.84-1.63 (m, 4H, CH₂CH ₂CH₂); 1.56-1.38 (m, 5H, CHCH₂CH₂, CHCH₂CH₂); 1.17-1.13 (m, 6H, CH₃).

¹³C NMR{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) 210.74-209.61 (C═O);48.78-45.42 ((CH₃)CHCH₂CH₂ CHS); 41.30-39.48 ((CH₃)CHCH₂ CH₂CHS);36.59-36.13 (CHCH₂CH₂CH₂); 28.26-27.94 (CHCH₂ CH₂CH₂); 15.38-14.45(CH₃).

Example 11: Synthesis of5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL 24) Accordingto the Process in Accordance with the Invention

1) First Step: Preparation of methyl13-hydroxy-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate(Xanthate XA2HN)

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropylS-(1-methoxycarbonyl)ethyl xanthate (XA2)

0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was addedto a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained abovein the preceding step 1.1) of example 1, in 200 ml of acetone(Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once theaddition had ended, the reaction medium was stirred at room temperaturefor 3 hours then filtered. The filtrate was concentrated under vacuum inorder to obtain the expected product XA2 in the form of a yellow oil (43g, yield 86%) which will be used in the following step withoutpurification.

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.51 (p, ³J_(H,H)=6.3 Hz, 1H,(CH₃)₂CHCH(O)CH₃); 4.42-4.30 (m, 1H, CH(CH₃)CO₂CH₃); 3.73 (s, 3H, CO₂CH₃); 2.09-1.88 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.56-1.52 (m, ³J_(H,H)=7.4 Hz,3H, CH(CH ₃)CO₂CH₃); 1.29-1.25 (m, ³J_(H,H)=6.4 Hz, 3H, (CH₃)₂CHCH(O)CH₃); 1.02-0.91 (m, 6H, (CH ₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 211.4; 211.4 (C═S); 172.0(CO₂CH₃); 86.2-86.1 ((CH₃)₂CHCH(O)CH₃); 52.8 (CO₂ CH₃); 46.5(CH(CH₃)CO₂CH₃); 32.7 ((CH₃)₂ CHCH(O)CH₃); 18.2-17.8 ((CH₃)₂CHCH(O)CH₃);17.0-16.9 (CH(CH₃)CO₂CH₃); 15.8-15.7 ((CH₃)₂CHCH(O)CH₃) ppm.

IR: 1738.5 cm⁻¹ (C═O); 1046.2 cm⁻¹ (C═S)

1.2) Sub-step 2: Preparation of methyl13-hydroxy-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate(XA2HN)

The xanthate XA2HN was prepared according to the same procedure as thatused above in step 1.2) of example 2 for the preparation of the xanthateXA2AP, but using 5.01 g (20 mmol) of the xanthate XA2 prepared in thepreceding step, 3.05 g (18 mmol) of undecene-1-ol (Sigma-Aldrich) and 1g (26 mmol) of LPO.

5.8 g of XA2HN were thus obtained (yellow oil; eluent hexane/ethylacetate (7:3; v:v), in the form of a racemate (yield 77%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ=5.57-5.48 (m, 1H, (CH₃)₂CHCH(O)CH₃);3.75-3.71 (m, 1H, SCHCH₂CH(CH₃)CO₂CH₃); 3.66-3.64 (m, 3H, CO₂CH₃);3.62,-3.57 (t, 2H, CH₂(CH₂)₆CH₂CH₂OH); 2.72-2.65 (m, 1H,SCHCH₂CH(CH₃)CO₂CH₃); 2.12-1.91 (m, 2H, SCHCH₂CH(CH₃)CO₂CH₃); 1.80 (s,1H, OH); 1.73-1.48 (m, 5H, (CH₃)₂CHCH(O)CH₃; CH₂(CH₂)₆CH₂CH₂OH);1.38-1.24 (m, 15H, CH(CH₃)CO₂CH₃; CH₂(CH₂)₆CH₂CH₂OH); 1.17-1.15 (m, 3H,(CH₃)₂CHCH(O)CH₃); 0.94-0.92 (m, 6H, (CH₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ=213.80-213.70 (C═S); 176.65(CO₂CH₃); 85.40 ((CH₃)₂CHCH(O)CH₃); 62.90 (CH₂(CH₂)₆CH₂ CH₂OH); 51.58(CO₂ CH₃); 49.14-48.59 (SCHCH₂CH(CH₃)CO₂CH₃); 38.16-37.54(SCHCH₂CH(CH₃)CO₂CH₃); 37.50-37.13 (SCHCH₂ CH(CH₃)CO₂CH₃); 32.70-32.69((CH₃)₂ CHCH(O)CH₃; CH₂(CH₂)₆ CH₂CH₂OH); 29.48-25.72(CH₂(CH₂)₆CH₂CH₂OH); 18.25-18.23 ((CH₃)₂CHCH(O)CH₃); 17.02-15.79((CH₃)₂CHCH(O)CH₃); CH(CH₃)CO₂CH₃).

2) Second Step: Preparation of5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one (TL24)

The thiolactone TL24 was prepared according to the same procedure asthat used above in example 2, step 3) for the preparation of thethiolactone TL2, but using 3.4 g (8 mmol) of the xanthate XA2HN preparedabove in the preceding step instead of the xanthate XA2AP.

1.89 g of thiolactone TL24 were thus obtained (yield 91%) in the form ofa colourless liquid (eluent: hexane/ethyl acetate: 5:5; v:v).

¹H NMR (300 MHz, CDCl₃, 298K) δ=3.74-3.63 (m, 1H, SCHCH₂CH); 3.58-3.53(t, 2H, SCHCH₂(CH₂)₆CH₂CH ₂OH); 2.72-2.43 (m, 1.5H, C(O)CH(CH₃)CH ₂);2.24 (s, 1H, OH); 2.15-1.95 (m, 1H, SCHCH ₂CH); 1.74-1.60 (m, 2H,CH₂(CH₂)₆CH ₂CH₂OH); 1.52-1.42 (m, 2.5H, SCHCH ₂CH, CH ₂(CH₂)₆CH₂CH₂OH);1.37-1.20 (m, 12H, CH₂(CH ₂)₆CH₂CH₂OH); 1.12-1.09 (m, 3H, C(O)CH(CH₃)CH₂).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ=211.34-210.18 (C═O); 62.78(CH₂(CH₂)₆CH₂ CH₂OH); 48.81-45.50 (SCHCH₂CH, C(O)CH(CH₃)CH₂);41.37-39.52 (SCHCH₂(CH₂)₆ CH₂CH₂OH); 36.71-36.36 (C(O)CH(CH₃)CH₂); 32.70(SCHCH₂(CH₂)₆CH₂CH₂OH); 29.45-25.73 (SCHCH₂(CH₂)₆CH₂CH₂OH); 15.38-14.42(C(O)CH(CH₃)CH₂).

Example 12: Synthesis of5-(9-bromononyl)-3-methyldihydrothiophen-2(3H)-one (TL25) According tothe Process in Accordance with the Invention

1) First Step: Preparation of methyl13-bromo-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate(Xanthate XA2BN)

1.1) Sub-Step 1: Preparation of O-1,2-dimethylpropylS-(1-methoxycarbonyl)ethyl xanthate (XA2)

0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was addedto a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained abovein the preceding step 1.1) of example 1, in 200 ml of acetone(Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once theaddition had ended, the reaction medium was stirred at room temperaturefor 3 hours then filtered. The filtrate was concentrated under vacuum inorder to obtain the expected product XA2 in the form of a yellow oil (43g, yield 86%) which will be used in the following step withoutpurification.

¹H NMR (300.13 MHz, CDCl₃, 298K) δ 5.51 (p, ³J_(H,H)=6.3 Hz, 1H,(CH₃)₂CHCH(O)CH₃); 4.42-4.30 (m, 1H, CH(CH₃)CO₂CH₃); 3.73 (s, 3H, CO₂CH₃); 2.09-1.88 (m, 1H, (CH₃)₂CHCH(O)CH₃); 1.56-1.52 (m, ³J_(H,H)=7.4 Hz,3H, CH(CH ₃)CO₂CH₃); 1.29-1.25 (m, ³J_(H,H)=6.4 Hz, 3H, (CH₃)₂CHCH(O)CH₃); 1.02-0.91 (m, 6H, (CH ₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ 211.4; 211.4 (C═S); 172.0(CO₂CH₃); 86.2-86.1 ((CH₃)₂CHCH(O)CH₃); 52.8 (CO₂ CH₃); 46.5(CH(CH₃)CO₂CH₃); 32.7 ((CH₃)₂ CHCH(O)CH₃); 18.2-17.8 ((CH₃)₂CHCH(O)CH₃);17.0-16.9 (CH(CH₃)CO₂CH₃); 15.8-15.7 ((CH₃)₂CHCH(O)CH₃) ppm.

IR: 1738.5 cm⁻¹ (C═O); 1046.2 cm⁻¹ (C═S)

1.2) Sub-Step 2: Preparation of methyl13-bromo-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)tridecanoate(XA2BN)

The xanthate XA2BN was prepared according to the same procedure as thatused above in step 1.2) of example 2 for the preparation of the xanthateXA2AP, but using 1.01 g (4 mmol) of the xanthate XA2 prepared in thepreceding step, 0.86 g (3.7 mmol) of bromo-11-undecene (Alfa-Aesar) and0.22 g (0.5 mmol) of LPO.

1.41 g of XA2BN were thus obtained (yellow oil; eluent hexane/ethylacetate (95:5; v:v), in the form of a racemate (yield 80%).

¹H NMR (300.13 MHz, CDCl₃, 298K) δ=5.59-5.52 (m, 1H, (CH₃)₂CHCH(O)CH₃);3.78-3.77 (m, 1H, SCHCH₂CH(CH₃)CO₂CH₃); 3.66-3.64 (m, 3H, CO₂CH ₃);3.41-3.36 (t, 2H, CH₂(CH₂)₆CH₂CH ₂Br); 2.70-2.63 (m, 1H,SCHCH₂CH(CH₃)CO₂CH₃); 2.08-1.91 (m, 2H, SCHCH ₂CH(CH₃)CO₂CH₃); 1.73-1.48(m, 5H, (CH₃)₂CHCH(O)CH₃; CH ₂(CH₂)₆CH ₂CH₂Br); 1.38-1.24 (m, 15H, CH(CH₃)CO₂CH₃, CH₂(CH ₂)₆CH₂CH₂Br); 1.17-1.15 (m, 3H, (CH₃)₂CHCH(O)CH ₃);0.94-0.92 (m, 6H, (CH ₃)₂CHCH(O)CH₃).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ=213.80-213.70 (C═S); 176.65(CO₂CH₃); 85.40 ((CH₃)₂CHCH(O)CH₃); 51.58 (CO₂ CH₃); 49.14-48.59(SCHCH₂CH(CH₃)CO₂CH₃); 38.16-37.54 (SCHCH₂CH(CH₃)CO₂CH₃); 37.50-37.13(SCHCH₂ CH(CH₃)CO₂CH₃); 34.90 (CH₂(CH₂)₆CH₂ CH₂Br); 32.70-32.69 ((CH₃)₂CHCH(O)CH₃; CH₂(CH₂)₆ CH₂CH₂Br); 29.48-25.72 (CH₂(CH₂)₆CH₂CH₂Br);18.25-18.23 ((CH₃)₂CHCH(O)CH₃); 17.02-15.79 ((CH₃)₂CHCH(O)CH₃);CH(CH₃)CO₂CH₃).

2) Second Step: Preparation of5-(9-bromononyl)-3-methyldihydrothiophen-2(3H)-one (TL25)

The thiolactone TL25 was prepared according to the same procedure asthat used above in example 2, step 3) for the preparation of thethiolactone TL2, but using 0.59 g (1.2 mmol) of the xanthate XA2BNprepared above in the preceding step instead of the xanthate XA2AP.

0.202 g of thiolactone TL25 were thus obtained (yield 52%) in the formof a colourless liquid (eluent: hexane/ethyl acetate: 9:1; v:v).

¹H NMR (300 MHz, CDCl₃, 298K) δ=3.79-3.66 (m, 1H, SCHCH₂CH); 3.42-3.38(t, 2H, SCHCH₂(CH₂)₆CH₂CH ₂Br); 2.74-2.49 (m, 1.5H, C(O)CH(CH₃)CH ₂);2.18-2.02 (m, 1H, SCHCH ₂CH); 1.89-1.59 (m, 4H, CH ₂(CH₂)₆CH ₂CH₂Br);1.37-1.20 (m, 13H, CH₂(CH ₂)₆CH₂CH₂Br); 1.12-1.09 (m, 3H, C(O)CH(CH₃)CH₂).

¹³C NMR{¹H} (75.47 MHz, CDCl₃, 298K) δ=211.05-209.91 (C═O); 48.82-45.0(SCHCH₂CH, C(O)CH(CH₃)CH₂); 41.40 (CH₂(CH₂)₆CH₂ CH₂Br); 39.56-39.52(SCHCH₂(CH₂)₆ CH₂CH₂Br); 36.76-36.40 (C(O)CH(CH₃)CH₂); 32.70(SCHCH₂(CH₂)₆CH₂CH₂Br); 29.45-25.73 (SCHCH₂(CH₂)₆CH₂CH₂Br); 15.38-14.42(C(O)CH(CH₃)CH₂).

Example 13: Synthesis of5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL 26)According to the Process in Accordance with the Invention

1) First Step: Preparation of the Monoadduct of Formula (IVa); XA2ED

The monoadduct XA2ED was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 8.01 g (3.2×10⁻² mol) of xanthate XA2 as prepared in step 1.2)of example 2, 1.25 g (1.5×10⁻² mol) of 1,5-hexadiene (Aldrich), 1.77 gof LPO, and a reaction solvent composed of 6 ml of toluene.

The monoadduct XA2ED obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 95:5,v:v).

3.79 g of XA2ED were thus obtained (yield 73%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 5.47-5.46 (s, 2H,(CH₃)₂CHCH(O)CH₃); 3.77-3.78 (m, 2H, SCHCH₂CH(CH₃)); 3.66-3.64 (m, 6H,CO₂CH₃); 2.73-2.61 (2H, m, SCHCH₂CH(CH₃)); 2.15-1.91 (m, 4H,SCHCH₂CH(CH₃)); 1.73-1.49 (m, 6H, (CH₃)₂CHCH(O)CH₃ etSCH(CH₂CH₂)CH₂CH(CH₃)); 1.28-1.23 (d, 3H, SCHCH₂CH(CH₃)); 1.17-1.15 (d,3H, (CH₃)₂CHCH(O)CH₃); 0.94-0.92 (m, 6H, (CH₃)₂CHCH(O)CH₃).

2) Second Step: Preparation of5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL26)

3.36 g (5.7 mmol) of XA2ED obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL26 thus obtainedin the form of a yellow oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 6:4 (v:v)).

1.2 g of TL26 were thus obtained in the form of a white powder (yield84%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS);2.75-2.43 (m, 2H, C(O)CH(CH₃)CH ₂CH); 2.20-1.99 (m, 2H, C(O)CH(CH₃)CH₂CH); 1.56-1.38 (m, 5H, CHCH₂CH₂, CHCH ₂CH₂); 1.17-1.13 (m, 6H, CH₃).

¹³C NMR{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) 210.74-209.61 (C═O);48.78-45.42 ((CH₃)CHCH₂CH₂ CHS); 41.30-39.48 ((CH₃)CHCH₂ CH₂CHS);36.59-36.13 (CHCH₂CH₂CH₂); 15.38-14.45 (CH₃).

Example 14: Synthesis of5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one) (TL 27)According to the Process in Accordance with the Invention

1) First Step: Preparation of a Monoadduct of Formula (IVa); XA2HD

The monoadduct XA2HD was prepared according to the procedure used abovein step 1.2) of example 2 for the preparation of the monoadduct XA2AP,but using 9.07 g (3.6×10⁻² mol) of xanthate XA2 as prepared in step 1.2)of example 2, 2.38 g (1.5×10⁻² mol) of 1,9-decadiene (Aldrich), 2.03 gof LPO, and a reaction solvent composed of 7 ml of toluene.

The monoadduct XA2HD obtained in the form of a viscous yellow oil waspurified by silica chromatography (eluent hexane/ethyl acetate: 90:10,v:v). 7.37 g of XA2HD were thus obtained (yield 68%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 5.58-5.49 (s, 2H,(CH₃)₂CHCH(O)CH₃); 3.77-3.78 (m, 2H, SCHCH₂CH(CH₃)); 3.66-3.64 (m, 6H,CO₂CH₃); 2.73-2.61 (2H, m, SCHCH₂CH(CH₃)); 2.15-1.91 (m, 4H,SCHCH₂CH(CH₃)); 1.73-1.28 (m, 14H, (CH₃)₂CHCH(O)CH₃ etSCH(CH₂CH₂CH₂CH₂CH₂CH₂)CHSH) et (CH₃)₂CHCH(O)CH₃); 1.28-1.23 (d, 3H,SCHCH₂CH(CH₃)); 1.17-1.15 (d, 3H, (CH₃)₂CHCH(O)CH₃); 0.94-0.92 (m, 6H,(CH₃)₂CHCH(O)CH₃).

2) Second Step: Preparation of5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one (TL27)

6.56 g (10.2 mmol) of XA2HD obtained above in the preceding step wereplaced in a sealed Schlenk tube under vacuum and brought to atemperature of 190° C. for 48 hours. The reaction mixture wassubsequently cooled to room temperature and the volatile compoundsformed were eliminated under vacuum. The thiolactone TL27 thus obtainedin the form of a yellow oil was subsequently purified on a silicachromatography column (eluent ethyl acetate/hexane: 7:3 (v:v)).

2.48 g of TL27 were thus obtained in the form of a white powder (yield77%).

¹H NMR (300.13 MHz, CDCl₃, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS);2.75-2.43 (m, 2H, C(O)CH(CH₃)CH ₂CH); 2.20-1.99 (m, 2H, C(O)CH(CH₃)CH₂CH); 1.78-1.64 (m, 4H, SCH(CH₂CH₂CH ₂CH ₂CH₂CH₂)CHSH) 1.53-1.38 (m, 9H,CHCH₂CH₂, SCH(CH ₂CH ₂CH₂CH₂CH ₂CH ₂)CHSH); 1.17-1.13 (m, 6H, CH₃).

¹³C NMR{¹H} (282.38 MHz, CDCl₃, 298K): δ (ppm) 210.74-209.61 (C═O);48.78-45.42 ((CH₃)CHCH₂ CHS); 41.30-39.48 ((CH₃)CHCH₂CHS); 36.71-36.36(SCH(CH₂ CH₂CH₂CH₂ CH₂ CH₂)CHSH); 28.34-28.16 (SCH(CH₂CH₂ CH₂CH₂CH₂CH₂)CHCHSH); 15.38-14.45 (CH₃).

1. Process for preparing substituted thiolactones of the followingformula (I):

wherein: A¹ and A², which are identical or different, represent ahydrogen atom or a fluorine atom, Y represents a hydrogen atom or agroup selected from alkyl, hydroxyalkyl, aryl and cyano groups, or apolymer chain; L is a linker arm, m is an integer equal to 0 or 1, Trepresents CH₂, —O— or —NR⁶—, in which R⁶ represents a hydrogen atom oran alkyl, aryl or aralkyl radical, optionally substituted by a groupselected from the groups: maleimide, a group of formula:

 in which the symbol # is the point of attachment of said group to R⁶and in which Y has the same meaning as that chosen for the radical Y ofthe formula (I), OH; P(O)(OR⁷)(OR^(7′)) in which the radicals R⁷ andR^(7′), which are identical or different, represent a hydrogen atom oran alkyl radical; C_(n)F_(2n+1) in which n is an integer ranging from 1to 20; SiR⁸ _(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which areidentical or different, represent a hydrogen atom or an alkyl radicaland p is an integer equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na;B(OR¹⁰)₂, in which the two radicals R¹⁰, which are identical ordifferent, represent a hydrogen atom, an alkyl radical or form acarbon-based ring with the two oxygen atoms to which they are bonded;OR¹¹, in which R¹¹ represents a hydrogen atom or an alkyl, aryl oraralkyl radical; O(C═O)R¹², in which R¹² represents a hydrogen atom oran alkyl, aryl or aralkyl radical; O(C═O)OR¹³, in which R¹³ represents ahydrogen atom or an alkyl, aryl or aralkyl radical;N⁺R¹⁴R^(14′)R^(14″)A⁻, in which the radicals R¹⁴, R^(14′) and R^(14″),which are identical or different, represent a hydrogen atom or an alkyl,aryl or aralkyl radical and A represents a chlorine or bromine atom;NR^(15′)(C═O)R¹⁵, in which the radicals R¹⁵ and R^(15′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical or are connected together and form a ring such as a pyrrolidoneor caprolactam ring; NR^(16′)(C═O)OR¹⁶, in which R¹⁶ et R^(16′), whichare identical or different, represent a hydrogen atom or an alkyl, arylor aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS;OCH₂-epoxy; COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl,aryl or aralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), whichare identical or different, represent a hydrogen atom or an alkyl oraryl radical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical;azide N₃ and alkyne, e is an integer equal to 0 or 1, wherein: 1) whenA¹=A²=H and e=0, then W represents a hydrogen atom and Z¹ represents agroup selected from the groups alkyl; aryl; P(O)(OR⁷)(OR^(7′)), in whichthe radicals R⁷ and R^(7′), which are identical or different, representa hydrogen atom or an alkyl radical; C_(n)F_(2n+1) in which n is aninteger ranging from 1 to 20; SiR⁸ _(p)(OR⁹)_(3-p), in which theradicals R⁸ and R⁹, which are identical or different, represent ahydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or2; BF₃M⁺, in which M=K or Na; B(OR¹⁰)₂, in which the two radicals R¹⁰,which are identical or different, represent a hydrogen atom, an alkylradical or form a carbon-based ring with the two oxygen atoms to whichthey are bonded; OR¹¹, in which R¹¹ represents a hydrogen atom or analkyl, aryl or aralkyl radical; O(C═O)R¹², in which R¹² represents ahydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)OR¹³, in whichR¹³ represents a hydrogen atom or an alkyl, aryl or aralkyl radical;N⁺R¹⁴R^(14′)R^(14″)A⁻, in which the radicals R¹⁴, R^(14′) and R^(14″),which are identical or different, represent a hydrogen atom or an alkyl,aryl or aralkyl radical and A represents a chlorine or bromine atom;NR^(15′)(C═O)R¹⁵, in which the radicals R¹⁵ and R^(15′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical or are connected together and form a ring such as a pyrrolidoneor caprolactam ring; NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), whichare identical or different, represent a hydrogen atom or an alkyl, arylor aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS;OCH₂-epoxy; COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl,aryl or aralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), whichare identical or different, represent a hydrogen atom or an alkyl oraryl radical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical;azide N₃ and alkyne; and a thiolactone ring of formula

 in which the symbol # is the point of attachment of the thiolactonering to L and in which Y has the same meaning as that chosen for theradical Y of the formula (I), 2) when A¹=A²=H, m=1 and e=0, then Wrepresents a hydrogen atom and Z¹ may also represent a hydrogen atom; 3)when A¹=A²=H, e=1 and m=0, then Z¹ and W are identical and represent—CH₂— or CO; 4) when A¹=A²=H, e=1, m=1 and T=CH₂, then Z¹=W=—CH₂, 5)when A¹=A²=F, e=0 and m=0, then W represents a fluorine atom and Z¹=F orrepresents a linear or branched chain OC_(q)F_(2q+1) in which q is aninteger ranging from 1 to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integerranging from 0 to 20, OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, orOCF₂CF(CF₃)OC₂F₄CO₂CH₃; and 6) when A¹=A²=F, e=1 and m=0, then W=Z¹=CF₂and T=(CF₂)_(s), with s=an integer ranging from 1 to 5; 7) when A¹=H,A²=F, and e=m=0, then W represents a hydrogen atom and Z¹=F orC_(n)F_(2n+1), in which n is an integer ranging from 1 to 20; whereinsaid process comprises at least the following steps: 1) a step duringwhich, in the presence of a radical initiator, a xanthate of thefollowing formula (II) is reacted:

wherein: R¹, R², R³ and R⁴, which are identical or different, representa hydrogen atom or a group chosen from saturated or unsaturatedheterocycloalkyl, alkyl, acyl, aryl, alkene, alkyne, cycloalkyl, orheterocycloaryl groups and polymer chains, it being understood that theradicals R¹, R², R³ and R⁴ may also form, together, a saturated,unsaturated or aromatic cycloalkyl or heterocycloalkyl group; it beingunderstood that at least one of the radicals R¹ and R³ is other than ahydrogen atom; Y has the same meaning as in the formula (I) above, Xrepresents NR²⁰, in which R²⁰ represents a hydrogen atom or an alkylradical or —O—, R⁵ is chosen from a saturated, unsaturated or aromaticheterocycloalkyl, alkyl, acyl, aryl, aralkyl or cycloalkyl group, with amonomer comprising an ethylenic unsaturation of the following formula(III):

wherein: A¹ and A², which are identical or different, represent ahydrogen atom or a fluorine atom, L, m, T and e have the same meaning asin the formula (I) above; wherein: 1) when A¹=A²=H and e=0, then Wrepresents a hydrogen atom and Z² represents a group selected from thegroups alkyl; aryl; P(O)(OR⁷)(OR^(7′)), in which the radicals R⁷ andR^(7′), which are identical or different, represent a hydrogen atom oran alkyl radical; C_(n)F_(2n+1), in which n is an integer ranging from 1to 20; SiR⁸ _(p)(OR⁹)_(3-p), in which the radicals R⁸ and R⁹, which areidentical or different, represent a hydrogen atom or an alkyl radicaland p is an integer equal to 0, 1 or 2; BF₃M⁺, in which M=K or Na;B(OR¹⁰)₂, in which the two radicals R¹⁰, which are identical ordifferent, represent a hydrogen atom, an alkyl radical or form acarbon-based ring with the two oxygen atoms to which they are bonded;OR¹¹, in which R¹¹ represents a hydrogen atom or an alkyl, aryl oraralkyl radical; O(C═O)R¹², in which R¹² represents a hydrogen atom oran alkyl, aryl or aralkyl radical; O(C═O)OR¹³, in which R¹³ represents ahydrogen atom or an alkyl, aryl or aralkyl radical;N⁺R¹⁴R^(14′)R^(14″)A⁻, in which the radicals R¹⁴, R^(14′) and R^(14″),which are identical or different, represent a hydrogen atom or an alkyl,aryl or aralkyl radical and A represents a chlorine or bromine atom;NR^(15′)(C═O)R¹⁵, in which the radicals R¹⁵ and R^(15′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical or are connected together and form a ring such as a pyrrolidoneor caprolactam ring; NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), whichare identical or different, represent a hydrogen atom or an alkyl, arylor aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS;OCH₂-epoxy; COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl,aryl or aralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), whichare identical or different, represent a hydrogen atom or an alkyl oraryl radical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical;azide N₃, alkyne and C₂H₃; 2) when A¹=A²=H, m=1 and e=0, then Wrepresents a hydrogen atom and Z² may also represent a hydrogen atom, 3)when A¹=A²=H, e=1 and m=0, then Z² and W are identical and represent—CH₂— or CO; 4) when A¹=A²=H, e=1, m=1 and T=CH₂, then Z²=W=—CH₂, 5)when A¹=A²=F, e=0 and m=0, then W represents a fluorine atom and Z²=F orrepresents a linear or branched chain OC_(q)F_(2q+1) in which q is aninteger ranging from 1 to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integerranging from 0 to 20, OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, orOCF₂CF(CF₃)OC₂F₄CO₂CH₃; and 6) when A¹=A²=F, e=1 and m=0, then W=Z²=CF₂and T=(CF₂)_(s), with s=an integer ranging from 1 to 5; 7) when A¹=H,A²=F, and e=m=0, then W represents a hydrogen atom and Z²=F orC_(n)F_(2n+1), in which n is an integer ranging from 1 to 20; to form amonoadduct of the following formula (IV):

wherein: A¹ and A², which are identical or different, represent ahydrogen atom or a fluorine atom, R¹, R², R³, R⁴, R⁵, X and Y have thesame meaning as in the formula (II) above, L, m, T and e have the samemeaning as in the formula (I) above, wherein: 1) when A¹=A²=H and e=0,then W represents a hydrogen atom and Z³ represents a group selectedfrom the groups alkyl; aryl; P(O)(OR⁷)(OR^(7′)), in which the radicalsR⁷ and R^(7′), which are identical or different, represent a hydrogenatom or an alkyl radical; C_(n)F_(2n+1), in which n is an integerranging from 1 to 20; SiR⁸ _(p)(OR⁹)_(3-p), in which the radicals R⁸ andR⁹, which are identical or different, represent a hydrogen atom or analkyl radical and p is an integer equal to 0, 1 or 2; BF₃M⁺, in whichM=K or Na; B(OR¹⁰)₂, in which the two radicals R¹⁰, which are identicalor different, represent a hydrogen atom, an alkyl radical or form acarbon-based ring with the two oxygen atoms to which they are bonded;OR¹¹, in which R¹¹ represents a hydrogen atom or an alkyl, aryl oraralkyl radical; O(C═O)R¹², in which R¹² represents a hydrogen atom oran alkyl, aryl or aralkyl radical; O(C═O)OR¹³, in which R¹³ represents ahydrogen atom or an alkyl, aryl or aralkyl radical;N⁺R¹⁴R^(14′)R^(14″)A⁻, in which the radicals R¹⁴, R^(14′) and R^(14″),which are identical or different, represent a hydrogen atom or an alkyl,aryl or aralkyl radical and A represents a chlorine or bromine atom;NR^(15′)(C═O)R¹⁵, in which the radicals R¹⁵ and R^(15′), which areidentical or different, represent a hydrogen atom or an alkyl or arylradical or are connected together and form a ring such as a pyrrolidoneor caprolactam ring; NR^(16′)(C═O)OR¹⁶, in which R¹⁶ and R^(16′), whichare identical or different, represent a hydrogen atom or an alkyl, arylor aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS;OCH₂-epoxy; COOR¹⁷, in which R¹⁷ represents a hydrogen atom, an alkyl,aryl or aralkyl radical; CONR¹⁸R^(18′), in which R¹⁸ and R^(18′), whichare identical or different, represent a hydrogen atom or an alkyl oraryl radical; SO₂R¹⁹, in which R¹⁹ represents an alkyl or aryl radical;azide N₃, alkyne, and a group of the following formula (V):

in which the symbol # is the point of attachment of the group of formula(V) to L and Y has the same meaning as that chosen for the radical Y offormula (IV), 2) when A¹=A²=H, m=1 and e=0, then W represents a hydrogenatom and Z³ may also represent a hydrogen atom, 3) when A¹=A²=H, e=1 andm=0, then Z³ and W are identical and represent —CH₂— or CO; 4) whenA¹=A²=H, e=1, m=1 and T=CH₂, then Z³=W=—CH₂, 5) when A¹=A²=F, e=0 andm=0, then W represents a fluorine atom and Z³=F or represents a linearor branched chain OC_(q)F_(2q+1) in which q is an integer ranging from 1to 5, [OCF₂CF(CF₃)]_(r)OC₃F₇, with r=an integer ranging from 0 to 20,OC₂F₄SO₂F, OCF₂CF(CF₃)OC₂F₄SO₂F, or OCF₂CF(CF₃)OC₂F₄CO₂CH₃; and 6) whenA¹=A²=F, e=1 and m=0, then W=Z³=CF₂ and T=(CF₂)_(s), with s=an integerranging from 1 to 5; 7) when A¹=H, A²=F, and e=m=0, then W represents ahydrogen atom and Z³=F or C_(n)F_(2n+1), in which n is an integerranging from 1 to 20; then 2) a step of thermolysis of the monoadduct offormula (IV) obtained above in the preceding step, to form acorresponding substituted thiolactone of formula (I).
 2. Processaccording to claim 1, wherein said process is carried out for thepreparation of thiolactones of formula (I) in which: Z¹ is a groupchosen from the groups P(O)(OR⁷)(OR^(7′)); C_(n)F_(2n+1); B(OR¹⁰)₂;OR¹¹; SiR⁸ _(p)(OR⁹)_(3-p); NR^(15′)(C═O)R¹⁵, in which R^(15′) is ahydrogen atom and NR^(16′)(C═O)OR¹⁶, in which R^(16′) is a hydrogenatom, and/or Y is a hydrogen atom or a group chosen from an alkylradical.
 3. Process according to claim 1, wherein said process iscarried out for the preparation of substituted thiolactones of formula(I) in which: Z¹ is a group chosen from the groups dimethylphosphonateand diethylphosphonate; C_(n)F_(2n+1); B(OR¹⁰)₂, OR¹¹, SiR⁸_(p)(OR⁹)_(3-p), NR^(15′)(C═O)R¹⁵, in which R^(15′) is a hydrogen atomand NR^(16′)(C═O)OR¹⁶, in which R^(16′) is a hydrogen atom, and/or Y isa hydrogen atom or a methyl or hydroxymethyl group.
 4. Process accordingto claim 1, wherein said process leads to the formation of a thiolactoneof formula (I), chosen from: dimethyl5-oxo-tetrahydrothiophen-2-ylphosphonate, diethyl(4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, diethyl(5-oxo-tetrahydrothiophen-2-yl)methylphosphonate,3-methyl-5-pentyl-dihydrothiophen-2(3H)-one,5-pentyl-dihydrothiophen-2(3H)-one,3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one,3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H, 5H)-trione,3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one,(4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid,((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid,(5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid,3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one,5-(trimethoxysilyl)dihydrothiophen-2(3H)-one,tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate,tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate,3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one,5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one,3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one,(5-oxo-tetrahydrothiophen-2-yl)phosphonic acid,5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one,5-(perfluorooctyl)dihydrothiophen-2(3H)-one,5-(perfluorobutyl)dihydrothiophen-2(3H)-one,dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one,5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one,5-(9-bromononyl)₃-methyldihydrothiophen-2(3H)-one,5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one, and5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one.
 5. Processaccording to claim 1, wherein the step 1) of preparation of themonoadduct of formula (IV) is carried out without solvent, in water orin an organic solvent.
 6. Process according to claim 1, wherein theradical initiator used during step 1) is chosen from organic peroxides,azo derivatives, redox couples that generate radicals and redox systems.7. Process according to claim 6, wherein the organic peroxides arechosen from dilauroyl peroxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t-butyl peroxyoctoate, t-butyl peroxydodecanoate,t-butyl peroxyisobutyrate, t-amyl peroxypivalate, t-butylperoxypivalate, diisopropyl peroxydicarbonate, dicyclohexylperoxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, potassiumperoxydisulfate, sodium peroxydisulfate and ammonium peroxydisulfate. 8.Process according to claim 1, wherein the linker arm L is a linear alkylchain, possibly interrupted by one or more heteroatoms, saidhydrocarbon-based chain having from 1 to 100 carbon atoms.
 9. Processaccording to claim 1, wherein the monomers of formula (III) are alkeneschosen from ethylene, propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, perfluorohexylethylene andperfluorooctylethylene.
 10. Process according to claim 1, wherein themonomers of formula (III) are allylic compounds chosen from allylicalcohol, N-allyl benzamide, ethyl N-allyl carbamate, tert-butyl N-allylcarbamate, 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,2-allyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione, allylboronic acid,diethyl allylphosphonate, allyl phosphonic dichloride, dimethylallylphosphonate, allyl cyanide, allyl isothiocyanate, allyl glycidylether, allyl benzyl ether, allyl phenyl ether, allyl butyl ether, allylethyl ether, allyl methylsulfone, allyl phenylsulfone, allyl chloride,allyl bromide and allyl fluoride.
 11. Process according to claim 1,wherein step 1) is carried out at a temperature varying from 10 to 140°C.
 12. Process according to claim 1, wherein step 2) of thermolysis iscarried out without solvent.
 13. Process according to claim 1, whereinat least one of the groups R¹ or R³ is other than a hydrogen atom. 14.Substituted thiolactones of the following formula (I′):

wherein: A′¹, A′², Y′, Z′, L′, m′, T′ and e′ may respectively assume thesame meanings as those defined in claim 1 for A¹, A², Y, Z¹, L, m, T ande for the thiolactones of formula (I), with the proviso that: when e′=0and W′=H and m′=0 and Y′=hydrogen, then Z^(1′) is other than a hydrogenatom, than a linear alkyl chain or than a phenyl ring; and when e′=0 andW′=H and m′=0 and Y′ is a substituent having a nitrogen atom directlybonded to the thiolactone ring, then Z^(1′) is other than a hydrogenatom.
 15. Substituted thiolactones of formula (I′) according to claim14, wherein they are chosen from: dimethyl5-oxo-tetrahydrothiophen-2-ylphosphonate, diethyl(4-methyl-5-oxo-tetrahydrothiophen-2-yl)methylphosphonate, diethyl(5-oxo-tetrahydrothiophen-2-yl)methylphosphonate,3-methyl-5-pentyl-dihydrothiophen-2(3H)-one,5-pentyl-dihydrothiophen-2(3H)-one,3-methyl-5-(perfluorooctyl)dihydrothiophen-2(3H)-one,3-methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H, 5H)-trione,3-methyl-5-(perfluorobutyl)dihydrothiophen-2(3H)-one,(4-methyl-5-oxo-tetrahydrothiophen-2-yl)phosphonic acid,((4-methyl-5-oxo-tetrahydrothiophen-2-yl)methyl)phosphonic acid,(5-oxo-tetrahydrothiophen-2-yl)methylphosphonic acid,3-methyl-5-(trimethoxysilyl)dihydrothiophen-2(3H)-one,5-(trimethoxysilyl)dihydrothiophen-2(3H)-one,tert-butyl-N-(4-methyl-5-oxo-tetrahydrothiophen-2-yl)carbamate,tert-butyl (5-oxotetrahydrothiophen-2-yl)carbamate,3-methyl-5-(oxiran-2-ylmethoxy)dihydrothiophen-2(2H)-one,5-((oxiran-2-yloxy)methyl)dihydrothiophen-2(3H)-one,3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one,(5-oxo-tetrahydrothiophen-2-yl)phosphonic acid,5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dihydrothiophen-2(3H)-one,5-(perfluorooctyl)dihydrothiophen-2(3H)-one,5-(perfluorobutyl)dihydrothiophen-2(3H)-one,dihydro-5-(3-(tetrahydro-4-methyl-5-oxothiophen-2-yl)propyl)-3-methylthiophen-2(3H)-one,5-(9-hydroxynonyl)-3-methyldihydrothiophen-2(3H)-one,5-(9-bromononyl)₃-methyldihydrothiophen-2(3H)-one,5,5′-(ethane-1,2-diyl)bis(3-methyldihydrothiophen-2(3H)-one, and5,5′-(hexane-1,6-diyl)bis(3-methyldihydrothiophen-2(3H)-one.
 16. Atleast one substituted thiolactone of formula (I) obtained according tothe process as defined in claim 1, said at least one substitutedthiolactone configured for the synthesis of polymers or for surfacefunctionalization or polymer functionalization.
 17. least onethiolactone of formula (I′) as defined in claim 14, said at least onesubstituted thiolactone configured for the synthesis of polymers or forsurface functionalization or polymer functionalization.